CN114752813A - Medical porous Ti-Mn-Cu alloy and preparation method thereof - Google Patents
Medical porous Ti-Mn-Cu alloy and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a medical porous Ti-Mn-Cu alloy and a preparation method thereof, belonging to the technical field of medical materials. The medical porous Ti-Mn-Cu alloy comprises the following components in percentage by mass: 1-15 wt% of manganese, 1-15 wt% of copper and 70-98 wt% of titanium, wherein the porosity of the medical porous Ti-Mn-Cu alloy is 25-70%, the porosity comprises macropores and micropores, the average pore diameter of the macropores is 100-600 mu m, the micropores are located on the wall of the macropores, and the pore diameter of the micropores is 1-99 mu m. The medical porous Ti-Mn-Cu alloy has the advantages of good biocompatibility, adjustable elastic modulus matched with bone tissues, easy preparation, low cost, antibacterial property and the like, and can be used as a bone defect repair material.
Description
Technical Field
The invention relates to a medical porous Ti-Mn-Cu alloy and a preparation method thereof, belonging to the technical field of medical materials.
Background
The titanium alloy has the advantages of good biocompatibility, high specific strength, good corrosion resistance when contacting with human body fluid and the like, and is commonly used as a bone repair material or a bone replacement material in clinic. Nevertheless, titanium alloys present some problems that can lead to the risk of clinical failure, such as the elastic modulus of titanium alloys being higher than the "stress shielding" effect produced by bone tissue leading to bone resorption; some medical titanium alloys currently used clinically, such as Ti-6Al-4V, Ti-5Al-2.5Fe, contain cytotoxic alloying elements such as Al, V, etc.; in addition, these titanium alloys lack antibacterial properties and are unable to prevent bacterial infection during implantation surgery and early recovery. Therefore, there is an urgent need to develop a medical titanium alloy having no toxicity, an elastic modulus matching with bone tissue, and antibacterial properties.
At present, researchers mainly develop beta or near beta type titanium alloy by adding nontoxic Nb, Ta, Mo, Zr and other alloy elements to relieve the stress shielding effect and avoid the cytotoxicity problem of the alloy elements, and the novel medical titanium alloy has no cytotoxicity and greatly reduces the elastic modulus. However, their elastic modulus is still higher than that of bone tissue, and the "stress shielding" effect still exists. Moreover, most of the added alloy elements are refractory metals with high melting points, so that the titanium alloy is difficult to prepare, and the titanium alloy contains a large amount of expensive alloy elements with limited sources, so that the prepared medical titanium alloy has high cost. In addition, these medical titanium alloys are deficient in antibacterial properties. At present, the antibacterial surface obtained by carrying out surface modification on the titanium alloy or preparing a coating on the surface of the titanium alloy has the risk of antibacterial property disappearance and the like caused by friction, abrasion and the like.
Disclosure of Invention
The first purpose of the invention is to provide a medical porous Ti-Mn-Cu alloy.
In order to achieve the first object of the present invention, the medical porous Ti-Mn-Cu alloy comprises the following components by mass: 1-15 wt% of manganese, 1-15 wt% of copper and 70-98 wt% of titanium, wherein the porosity of the medical porous Ti-Mn-Cu alloy is 25-70%, the porosity comprises macropores and micropores, the average pore diameter of the macropores is 100-600 mu m, the micropores are located on the wall of the macropores, and the pore diameter of the micropores is 1-99 mu m.
In one specific embodiment, the medical porous Ti-Mn-Cu alloy consists of the following components in percentage by mass: 3-10 wt% of manganese, 3-10 wt% of copper and 80-94 wt% of titanium.
In a specific embodiment, the medical porous Ti-Mn-Cu alloy has the elastic modulus of 1.1GPa to 11.8GPa and the compressive strength of 26MPa to 760 MPa; preferably, the elastic modulus is 1.5GPa to 11.8GPa, and the compressive strength is 42MPa to 760 MPa.
In one embodiment, the preparation method of the medical porous Ti-Mn-Cu alloy comprises the following steps:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed blank dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
In a specific embodiment, the mixing in the step a is carried out on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/min, and the ball-milling time is 1-8 h; and a, drying at the temperature of 40-80 ℃ for 6-12 h, preferably 10 h.
In a specific embodiment, the particle size of the ammonium bicarbonate particles in the step b is 100-600 μm, preferably 300-600 μm; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; and b, preferably, manually mixing the mixture in the step b, wherein the mixing time is 5-10 min.
In a specific embodiment, the pressing in the step c is performed at 100-300 MPa for 1-5 min to obtain a pressed blank; the green compact drying temperature is 40-80 ℃, and the drying time is 6-12 h.
In a specific embodiment, the vacuum sintering in step d is three-stage temperature rising and heat preservation sintering: at 10-1～10-3Heating the first section to 150-300 ℃ at a speed of 3-10 ℃/min under a vacuum condition of Pa, and preserving heat for 1-3 h; the temperature is raised to 700-800 ℃ at a rate of 3-10 ℃/min in the second section, the temperature is maintained for 10-60 min, the temperature is raised to 850-1050 ℃ at a rate of 3-5 ℃/min in the third section, and the temperature is maintained for 1-3 h.
The second purpose of the invention is to provide a preparation method of the medical porous Ti-Mn-Cu alloy.
In order to achieve the second object of the invention, the preparation method of the medical porous Ti-Mn-Cu alloy comprises the following steps:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed blank dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
In a specific embodiment, the mixing in the step a is carried out on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/min, and the ball-milling time is 1-8 h; the drying temperature in the step a is 40-80 ℃, and the drying time is 6-12 hours, preferably 10 hours;
the particle size of the ammonium bicarbonate particles in the step b is 100-600 microns, and preferably 300-600 microns; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; the mixing in the step b is preferably manual mixing, and the mixing time is 5-10 min;
c, the pressing in the step is 100-300 MPa, and the pressure is maintained for 1-5 min to obtain a pressed blank; drying the pressed blank at the temperature of 40-80 ℃ for 6-12 h;
and d, the vacuum sintering in the step d is three-stage heating and heat preservation sintering: at 10-1～10-3Heating the first section to 150-300 ℃ at a speed of 3-10 ℃/min under a vacuum condition of Pa, and preserving heat for 1-3 h; the temperature is raised to 700-800 ℃ at a rate of 3-10 ℃/min in the second section, the temperature is maintained for 10-60 min, the temperature is raised to 850-1050 ℃ at a rate of 3-5 ℃/min in the third section, and the temperature is maintained for 1-3 h.
Has the advantages that:
the medical porous Ti-Mn-Cu alloy has the advantages of good biocompatibility, adjustable elastic modulus matched with bone tissues, easy preparation, low cost, antibacterial property and the like, and can be used as a bone defect repair material. The concrete points are as follows:
(1) the invention selects the microelements manganese and copper which are necessary for human body as alloying elements, thereby avoiding the toxicity problem of the alloying elements, and the prepared medical porous Ti-Mn-Cu alloy has good biocompatibility;
(2) the mechanical property of the medical porous Ti-Mn-Cu alloy can be adjusted to be matched with bone tissues, so that the stress shielding effect can be reduced or eliminated, and the service life of the medical porous Ti-Mn-Cu alloy is prolonged;
(3) the porosity of the medical porous Ti-Mn-Cu alloy is adjustable within 25-70%, the pore diameter of a macropore of the medical porous Ti-Mn-Cu alloy is mainly distributed within 100-600 mu m, and the medical porous Ti-Mn-Cu alloy is suitable for a new bone tissue to grow into pores, so that the new bone tissue and the new bone tissue form stable fixation; micropores with the diameter of 1-99 mu m on the walls of the macropores can promote cell adhesion, proliferation and differentiation;
(4) The selected alloy elements of manganese (melting point: 1244 ℃) and copper (melting point: 1083 ℃) have relatively low melting points, and the preparation of the medical porous Ti-Mn-Cu alloy is easier; the alloy elements of manganese and copper have wide sources, so that the medical porous Ti-Mn-Cu alloy has low cost;
(5) the medical porous Ti-Mn-Cu alloy contains antibacterial copper, so that the whole medical porous Ti-Mn-Cu alloy has antibacterial property, and can avoid infection caused by implanted materials in and early in an operation. Meanwhile, the problem that the antibacterial property of the antibacterial surface obtained by the subsequent treatment of the current titanium alloy disappears for some reasons is solved.
Drawings
FIG. 1 is a scanning electron microscope image of the medical porous Ti-5Mn-3Cu alloy of example 1;
FIG. 2 scanning electron micrograph of medical porous Ti-5Mn-5Cu alloy of example 2.
Detailed Description
In order to achieve the first object of the present invention, the medical porous Ti-Mn-Cu alloy comprises the following components by mass: 1-15 wt% of manganese, 1-15 wt% of copper and 70-98 wt% of titanium, wherein the porosity of the medical porous Ti-Mn-Cu alloy is 25-70%, the porosity comprises macropores and micropores, the average pore diameter of the macropores is 100-600 mu m, the micropores are located on the wall of the macropores, and the pore diameter of the micropores is 1-99 mu m.
In one specific embodiment, the medical porous Ti-Mn-Cu alloy consists of the following components in percentage by mass: 3-10 wt% of manganese, 3-10 wt% of copper and 80-94 wt% of titanium.
In a specific embodiment, the medical porous Ti-Mn-Cu alloy has the elastic modulus of 1.1GPa to 11.8GPa and the compressive strength of 26MPa to 760 MPa; the elastic modulus is preferably 1.5GPa to 11.8GPa, and the compressive strength is preferably 42MPa to 760 MPa.
In a specific embodiment, the preparation method of the medical porous Ti-Mn-Cu alloy comprises the following steps:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed blank dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
In a specific embodiment, the mixing in the step a is carried out on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/min, and the ball-milling time is 1-8 h; and a, drying at the temperature of 40-80 ℃ for 6-12 h, preferably 10 h.
In a specific embodiment, the particle size of the ammonium bicarbonate particles in step b is 100 to 600 μm, preferably 300 to 600 μm; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; and b, preferably, manually mixing the mixture in the step b, wherein the mixing time is 5-10 min.
In a specific embodiment, the pressing in the step c is 100 to 300MPa, and the pressure is maintained for 1 to 5min to obtain a pressed blank; the green compact drying temperature is 40-80 ℃, and the drying time is 6-12 h.
In a specific embodiment, the vacuum sintering in step d is three-stage temperature rising and heat preservation sintering: at 10-1～10-3Heating to 150-300 ℃ at a speed of 3-10 ℃/min in the first stage under the vacuum condition of Pa, and preserving heat for 1-3 h; the temperature is raised to 700-800 ℃ at a rate of 3-10 ℃/min in the second section, the temperature is maintained for 10-60 min, the temperature is raised to 850-1050 ℃ at a rate of 3-5 ℃/min in the third section, and the temperature is maintained for 1-3 h.
In order to achieve the second object of the invention, the preparation method of the medical porous Ti-Mn-Cu alloy comprises the following steps:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed compact dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
In a specific embodiment, the mixing in the step a is carried out on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/m, and the ball-milling time is 1-8 h; the drying temperature in the step a is 40-80 ℃, and the drying time is 6-12 h, preferably 10 h;
the particle size of the ammonium bicarbonate particles in the step b is 100-600 microns, and preferably 300-600 microns; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; the mixing in the step b is preferably manual mixing, and the mixing time is 5-10 min;
c, the pressing in the step is 100-300 MPa, and the pressure is maintained for 1-5 min to obtain a pressed blank; drying the pressed blank at the temperature of 40-80 ℃ for 6-12 h;
and d, the vacuum sintering in the step d is three-stage heating and heat preservation sintering: at 10-1～10-3Heating the first section to 150-300 ℃ at a speed of 3-10 ℃/min under a vacuum condition of Pa, and preserving heat for 1-3 h; the temperature is raised to 700-800 ℃ at a rate of 3-10 ℃/min in the second section, the temperature is maintained for 10-60 min, the temperature is raised to 850-1050 ℃ at a rate of 3-5 ℃/min in the third section, and the temperature is maintained for 1-3 h.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the invention to the embodiments described.
Example 1
Weighing 2.5g of manganese powder with the granularity of 400 meshes, 1.5g of copper powder with the granularity of 400 meshes and 46g of titanium powder with the granularity of 325 meshes according to the liquid-solid ratio of 1.2 ml: adding absolute ethyl alcohol into 1g of the mixture, grinding the mixture on a planet ball mill for 2 hours at a ball material ratio of 10:1 at a speed of 300 revolutions per minute,drying at 60 ℃ for 10h to obtain Ti-Mn-Cu mixed powder. Weighing 4g of mixed powder, adding 4g of ammonium bicarbonate particles, uniformly mixing, adding 5 wt% of polyvinyl alcohol solution according to 0.01ml/g of powder, and uniformly mixing again; the mixture was charged into a forming die and pressed under 165MPa for 3min to obtain a green compact. The green compact was dried in a graphite crucible at 60 ℃ for 10 hours and then vacuum sintered. The whole is sintered at 10-1～10-3The preparation method comprises the steps of Pa vacuum degree, heating to 200 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 0.5h, heating to 1000 ℃ at the speed of 3 ℃/min, keeping the temperature for 2h, and cooling to room temperature to obtain the medical porous Ti-5Mn-3Cu alloy. The porosity of the medical porous Ti-Mn-Cu alloy is 62.49%, the elastic modulus is 2.93GPa, and the compressive strength is 97.67 MPa.
Example 2
Weighing 2.5g of manganese powder with the granularity of 400 meshes, 2.5g of copper powder with the granularity of 400 meshes and 45g of titanium powder with the granularity of 325 meshes according to the liquid-solid ratio of 1.2 ml: adding 1g of absolute ethyl alcohol, ball-material ratio of 10:1, ball-milling the mixed material for 2h at 300 revolutions per minute on a planet ball mill, and drying for 10h at 60 ℃ to obtain Ti-Mn-Cu mixed powder. Weighing 4g of mixed powder, adding 4g of ammonium bicarbonate particles, uniformly mixing, adding 5 wt% of polyvinyl alcohol solution according to 0.01ml/g of powder, and uniformly mixing again; the mixture was charged into a forming die and pressed under 165MPa for 3min to obtain a green compact. The green compact was dried in a graphite crucible at 60 ℃ for 10 hours and then vacuum sintered. The whole is sintered at 10-1～10-3The preparation method comprises the steps of Pa vacuum degree, heating to 200 ℃ at the speed of 5 ℃/min, keeping the temperature for 2h, heating to 800 ℃ at the speed of 5 ℃/min, keeping the temperature for 0.5h, heating to 1000 ℃ at the speed of 3 ℃/min, keeping the temperature for 2h, and cooling to room temperature to obtain the medical porous Ti-5Mn-5Cu alloy. The porosity of the medical porous Ti-Mn-Cu alloy is 60.71%, the elastic modulus is 3.02GPa, and the compressive strength is 117.75 MPa.
Example 3
Weighing 2.5g of manganese powder with the granularity of-400 meshes, 5g of copper powder with the granularity of-400 meshes and 42.5g of titanium powder with the granularity of-325 meshes according to the liquid-solid ratio of 1.2 ml: adding 1g of absolute ethyl alcohol, ball-material ratio of 10:1, mixing materials on a planetary ball mill at 300 revolutions/minute for 2h, and drying at 60 ℃ for 10h to obtain Ti-Mn-Cu mixture And (5) mixing the powder. Weighing 4g of mixed powder, adding 4g of ammonium bicarbonate particles, uniformly mixing, adding 5 wt% polyvinyl alcohol solution according to 0.01ml/g of powder, and uniformly mixing again; the mixture was charged into a forming die and pressed under 165MPa for 3min to obtain a green compact. The green compact was dried in a graphite crucible at 60 ℃ for 10 hours and then vacuum sintered. The whole is sintered at 10-1～10-3And (2) Pa vacuum degree, heating to 200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, heating to 1000 ℃ at the speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the medical porous Ti-5Mn-10Cu alloy. The porosity of the medical porous Ti-Mn-Cu alloy is 58.16%, the elastic modulus is 3.55GPa, and the compressive strength is 124.28 MPa.
Example 4
Weighing 5g of manganese powder with the granularity of-400 meshes, 2.5g of copper powder with the granularity of-400 meshes and 42.5g of titanium powder with the granularity of-325 meshes according to the liquid-solid ratio of 1.2 ml: adding 1g of absolute ethyl alcohol, ball-material ratio of 10:1, ball-milling the mixed material for 2h at 300 revolutions per minute on a planet ball mill, and drying for 10h at 60 ℃ to obtain Ti-Mn-Cu mixed powder. Weighing 4g of mixed powder, adding 4g of ammonium bicarbonate particles, uniformly mixing, adding 5 wt% polyvinyl alcohol solution according to 0.01ml/g of powder, and uniformly mixing again; the mixture was charged into a forming die and pressed under 165MPa for 3min to obtain a green compact. The green compact was dried in a graphite crucible at 60 ℃ for 10 hours and then vacuum sintered. The whole is sintered at 10 -1～10-3And (2) Pa vacuum degree, heating to 200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, heating to 1000 ℃ at the speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the medical porous Ti-10Mn-5Cu alloy. The porosity of the medical porous Ti-Mn-Cu alloy is 60.13%, the elastic modulus is 3.36GPa, and the compressive strength is 118.77 MPa.
Example 5
Weighing 1.5g of manganese powder with the granularity of-400 meshes, 1.5g of copper powder with the granularity of-400 meshes and 47g of titanium powder with the granularity of-325 meshes according to the liquid-solid ratio of 1.2 ml: adding 1g of absolute ethyl alcohol, ball-material ratio of 10:1, ball-milling the mixed material for 2h at 300 revolutions per minute on a planet ball mill, and drying for 10h at 60 ℃ to obtain Ti-Mn-Cu mixed powder. 8g of the mixed powder was weighed out,adding 2g of ammonium bicarbonate particles, uniformly mixing, adding 5 wt% polyvinyl alcohol solution according to 0.01ml/g of powder, and uniformly mixing again; the mixture was charged into a forming die and pressed under 165MPa for 3min to obtain a green compact. The green compact was dried in a graphite crucible at 60 ℃ for 10 hours and then vacuum sintered. The whole is sintered at 10-1～10-3And (2) Pa vacuum degree, heating to 200 ℃ at the speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the speed of 5 ℃/min, preserving heat for 0.5h, heating to 1000 ℃ at the speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature to obtain the medical porous Ti-3Mn-3Cu alloy. The porosity of the medical porous Ti-Mn-Cu alloy is 32.25%, the elastic modulus is 10.28GPa, and the compressive strength is 580.36 MPa.
Claims (10)
1. The medical porous Ti-Mn-Cu alloy is characterized by comprising the following components in percentage by mass: 1-15 wt% of manganese, 1-15 wt% of copper and 70-98 wt% of titanium, wherein the porosity of the medical porous Ti-Mn-Cu alloy is 25-70%, the porosity comprises macropores and micropores, the average pore diameter of the macropores is 100-600 mu m, the micropores are located on the wall of the macropores, and the pore diameter of the micropores is 1-99 mu m.
2. The medical porous Ti-Mn-Cu alloy according to claim 1, characterized in that it consists of the following components in mass percent: 3-10 wt% of manganese, 3-10 wt% of copper and 80-94 wt% of titanium.
3. The medical porous Ti-Mn-Cu alloy according to claim 1 or 2, wherein the medical porous Ti-Mn-Cu alloy has an elastic modulus of 1.1GPa to 11.8GPa and a compressive strength of 26MPa to 760 MPa; the elastic modulus is preferably 1.5GPa to 11.8GPa, and the compressive strength is preferably 42MPa to 760 MPa.
4. The medical porous Ti-Mn-Cu alloy according to claim 1 or 2, wherein the preparation method of the medical porous Ti-Mn-Cu alloy comprises:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed blank dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
5. The medical porous Ti-Mn-Cu alloy according to claim 4, wherein the mixing in the step a is performed on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/min, and the ball-milling time is 1-8 h; and a, drying at the temperature of 40-80 ℃ for 6-12 h, preferably 10 h.
6. The medical porous Ti-Mn-Cu alloy according to claim 4 or 5, wherein the particle size of the ammonium bicarbonate particles in step b is 100 to 600 μm, preferably 300 to 600 μm; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; and b, the mixing in the step b is preferably manual mixing, and the mixing time is 5-10 min.
7. The medical porous Ti-Mn-Cu alloy according to claim 4 or 5, wherein the pressing in the step c is performed at 100 to 300MPa for 1 to 5min to obtain a green compact; the green compact drying temperature is 40-80 ℃, and the drying time is 6-12 h.
8. The medical porous Ti-Mn-Cu alloy according to claim 4 or 5, wherein the vacuum sintering in step d is three-stage temperature raising and heat preservationAnd (3) warm sintering: at 10-1～10-3Heating to 150-300 ℃ at a speed of 3-10 ℃/min in the first stage under the vacuum condition of Pa, and preserving heat for 1-3 h; the temperature is raised to 700-800 ℃ at a rate of 3-10 ℃/min in the second section, the temperature is maintained for 10-60 min, the temperature is raised to 850-1050 ℃ at a rate of 3-5 ℃/min in the third section, and the temperature is maintained for 1-3 h.
9. The method for preparing the medical porous Ti-Mn-Cu alloy according to any one of claims 1 to 8, wherein the method comprises:
a, weighing titanium powder, manganese powder and copper powder with the granularity of less than 300 meshes, uniformly mixing, and drying to obtain Ti-Mn-Cu mixed powder;
b, mixing the Ti-Mn-Cu mixed powder obtained in the step a with ammonium bicarbonate particles and a binder to obtain a mixture, wherein the mass ratio of the ammonium bicarbonate particles to the Ti-Mn-Cu mixed powder is (20-60): 80-40 parts of; preferably, the Ti-Mn-Cu mixed powder in the step a is mixed with ammonium bicarbonate particles firstly, and then is mixed with a binder to obtain a mixture;
c, pressing and forming the mixture obtained in the step b to obtain a pressed blank, and drying the pressed blank;
and d, sintering the pressed compact dried in the step c in vacuum, and cooling to obtain the medical porous Ti-Mn-Cu alloy.
10. The preparation method of the medical porous Ti-Mn-Cu alloy according to claim 9, wherein the mixing in the step a is performed on a ball mill, absolute ethyl alcohol is used as a ball milling medium, and the liquid-solid ratio is 1-3 ml/g powder; the grinding balls are preferably stainless steel balls or hard alloy balls, the ball-material ratio is 5-10: 1, the rotating speed is 100-300 r/m, and the ball-milling time is 1-8 h; the drying temperature in the step a is 40-80 ℃, and the drying time is 6-12 h, preferably 10 h;
the particle size of the ammonium bicarbonate particles in the step b is 100-600 microns, and preferably 300-600 microns; the binder is preferably a polyvinyl alcohol solution, the mass concentration is 2-10%, and the dosage of the mixed powder per gram is 0.01-0.5 ml; the mixing in the step b is preferably manual mixing, and the mixing time is 5-10 min;
c, keeping the pressure of 100-300 MPa for 1-5 min to obtain a pressed blank; drying the pressed blank at the temperature of 40-80 ℃ for 6-12 h;
and d, the vacuum sintering in the step d is three-stage heating and heat preservation sintering: at 10 -1～10-3Heating to 150-300 ℃ at a speed of 3-10 ℃/min in the first stage under the vacuum condition of Pa, and preserving heat for 1-3 h; the temperature of the second section is raised to 700-800 ℃ at a rate of 3-10 ℃/min, the temperature is maintained for 10-60 min, the temperature of the third section is raised to 850-1050 ℃ at a rate of 3-5 ℃/min, and the temperature is maintained for 1-3 h.
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