CN112853143A - Porous titanium copper/hydroxyapatite composite material and preparation method thereof - Google Patents
Porous titanium copper/hydroxyapatite composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a porous titanium copper/hydroxyapatite composite material and a preparation method thereof, belonging to the technical field of biomedical materials. The preparation method of the porous titanium copper/hydroxyapatite composite material comprises the following steps: uniformly mixing titanium powder and copper powder with the particle size of less than 200 meshes to obtain titanium-copper mixed powder; uniformly mixing the titanium-copper mixed powder with hydroxyapatite powder with the granularity of less than 150 meshes; mixing stearic acid, a binder and the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture; pressing and forming the mixture to obtain a pressed blank; sintering the pressed compact in a vacuum environment, and cooling to obtain the porous titanium copper/hydroxyapatite composite material after sintering; wherein, the copper accounts for 5-25 wt%, the hydroxyapatite accounts for 5-30 wt%, and the titanium accounts for 45-90 wt%. The composite material has the advantages of good mechanical property, antibacterial property and bioactivity, and can be used as an implant material for repairing bone defects.
Description
Technical Field
The invention relates to a porous titanium copper/hydroxyapatite composite material and a preparation method thereof, belonging to the technical field of biomedical materials.
Background
Porous titanium has many advantages as a bone implant material, such as good strength, an elastic modulus similar to that of bone tissue, good biocompatibility, a porous structure that can provide biological fixation through bone tissue ingrowth, and the like. However, despite the strict aseptic procedure used during surgery and the use of antibiotics after surgery, the average bacterial infection after implantation of orthopedic implant materials is still as high as 2-5%. Bacterial infection can cause loosening of the implanted material resulting in implant failure.
The development of implant materials that have antimicrobial properties in themselves is an effective way to reduce bacterial infections and an urgent need. Currently there are mainly two approaches to achieve this: one is to modify the surface of titanium to obtain surface antibacterial property, but once the antibacterial surface is damaged by some reasons, the antibacterial property disappears; and secondly, adding an alloy element with antibacterial property to develop a novel titanium alloy with integral antibacterial property. For example, by adding Cu or Ag element having antibacterial property, an antibacterial titanium alloy having excellent antibacterial property can be prepared. When the porous titanium is prepared, Cu or Ag is added as an alloying element, so that the strength of the porous titanium can be increased, and the use safety of the porous titanium is improved. Compared with silver, copper is a necessary trace element for human bodies, and the cost is low. Therefore, the porous titanium-copper alloy has wide clinical application prospect as an antibacterial orthopedic implant material. However, the porous titanium-copper alloy lacks bioactivity, and cannot form strong chemical bond with surrounding bone tissues when being implanted, and the implant material may loosen after long-term use. Thus, there is a need to impart biological activity to porous titanium copper alloys to improve the ability to bond to the surrounding bone tissue.
Hydroxyapatite (HA) HAs chemical components and crystal structures similar to apatite in natural bones, HAs good biocompatibility with human bone tissues and bioactivity, is one of the most attractive biological ceramic materials for implanting into human hard tissues, but HAs poor mechanical properties so that the application of the HA is limited. The hydroxyapatite coating prepared on the surface of titanium and titanium alloy by adopting methods of plasma spraying, laser cladding and the like improves the bioactivity of the titanium and the titanium alloy, but the difference of the physical property and the thermal property of the titanium and the titanium alloy can cause the problems of coating shedding, degradation and the like.
Disclosure of Invention
The first problem to be solved by the invention is to provide a preparation method of a porous titanium copper/hydroxyapatite composite material.
In order to solve the first technical problem of the present invention, the preparation method of the porous titanium copper/hydroxyapatite composite material comprises:
(1) preparing titanium copper mixed powder: uniformly mixing titanium powder and copper powder with the particle size of less than 200 meshes to obtain titanium-copper mixed powder; the blending method is preferably as follows: ball-milling and uniformly mixing by a wet method, and drying at a preferable temperature of 40-80 ℃;
(2) preparing titanium copper/hydroxyapatite mixed powder: uniformly mixing the titanium-copper mixed powder obtained in the step (1) with hydroxyapatite powder with the granularity of below 150 meshes;
(3) mixing stearic acid, a binder and mixed powder: mixing stearic acid, a binder and the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture; preferably, stearic acid and the binder are mixed firstly, and then are mixed with the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture;
(4) and (3) pressing and forming: pressing and forming the mixture obtained in the step (3) to obtain a pressed blank;
(5) and (3) vacuum sintering: sintering the pressed compact in a vacuum environment, and cooling to obtain the porous titanium copper/hydroxyapatite composite material after sintering;
wherein, the copper accounts for 5-25 wt%, the hydroxyapatite accounts for 5-30 wt%, and the titanium accounts for 45-90 wt%.
The drying in the step (1) can be carried out in a constant-temperature drying oven, the drying temperature has influence on the product performance, the drying temperature is too high, and the powder can be oxidized, generally at 40-80 ℃.
In a specific embodiment, the medium for wet ball milling in step (1) is absolute ethyl alcohol, the liquid-solid ratio of wet ball milling is preferably 1-3: 1ml/g, the grinding balls for wet ball milling are preferably stainless steel balls or hard alloy balls, the ball-material ratio of wet ball milling is preferably 5-12: 1, the ball milling time of wet ball milling is preferably 1-8 h, and the rotation speed of wet ball milling is preferably 100-300 rpm.
In a specific embodiment, the mixing time in the step (2) is 5-20 min, and the mixing is manual mixing or mechanical stirring.
In a specific embodiment, the binder in step (3) is a polyvinyl alcohol solution with a mass concentration of 2-10%, the amount of the binder is preferably 0.01-0.2 ml/g mixed powder, the mixing time is preferably 5-20 min, and the mixing in step (3) is preferably manual mixing.
In one embodiment, the particle size of the stearic acid in the step (3) is 100 to 600 μm, and the addition amount of the stearic acid is preferably 10 to 30: 90-70.
In a specific embodiment, the pressure of the molding in the step (4) is 150 to 500MPa, and the pressure maintaining time is 1 to 5 min; preferably, the green compact is then dried.
In one embodiment, the vacuum sintering process in step (5) is: the vacuum degree is kept at 10-1～10-3Pa, heating to 150-300 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 1-3 h, then heating to 400-600 ℃ at 3-10 ℃/min, preserving heat for 1-3 h, then heating to 700-800 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 10-60 min, and finally preserving heat for 3-up toHeating to 800-1000 ℃ at a heating rate of 5 ℃/min, and preserving heat for 1-3 h.
The second technical problem to be solved by the invention is to provide a novel porous titanium copper/hydroxyapatite composite material.
In order to solve the second technical problem of the invention, the porous titanium copper/hydroxyapatite composite material comprises the following components: 5-25 wt% of copper, 5-30 wt% of hydroxyapatite, 45-90 wt% of titanium and inevitable impurities.
In a specific embodiment, the porous titanium copper/hydroxyapatite composite material is prepared by the method.
In a specific embodiment, the porosity of the porous titanium copper/hydroxyapatite composite material is adjustable within 27.6-60.9%, and the preferred macropore diameter of the porous titanium copper/hydroxyapatite composite material is 100-400 μm.
In a specific embodiment, the compressive strength of the porous titanium copper/hydroxyapatite composite material is 12.9-220.0 MPa, and the elastic modulus is preferably 0.4-5.0 GPa.
Has the advantages that:
(1) the invention adopts stearic acid as pore-forming agent, which can volatilize and decompose into gas to be discharged during vacuum sintering, and leaves pores, thus not polluting the prepared porous titanium copper/hydroxyapatite composite material.
(2) The porosity of the prepared porous titanium copper/hydroxyapatite composite material is adjustable within 27.6-60.9%, the pore diameter of a large pore is 100-400 microns, the porous titanium copper/hydroxyapatite composite material is suitable for bone tissues to grow into the pore, and the bonding strength between an implant material and the bone tissues is improved through biological fixation.
(3) The mechanical property of the prepared porous titanium copper/hydroxyapatite composite material can be adjusted to be matched with bone tissues, the compressive strength is 12.9-220.0 MPa, the elastic modulus is 0.4-5.0 GPa, the stress shielding effect is reduced or eliminated, and the service life of the implant is prolonged.
(4) The prepared porous titanium copper/hydroxyapatite composite material has antibacterial property and bioactivity, can reduce infection caused by an implanted material, can form chemical bond combination with bone tissues, and is favorable for forming stable fixation.
(5) The composite material has the advantages of good mechanical property, antibacterial property and bioactivity, and can be used as an implant material for repairing bone defects.
Drawings
FIG. 1 is a scanning electron microscope image of the pores of the porous titanium copper/hydroxyapatite composite material; (a, b, c are the porous titanium copper/hydroxyapatite composite materials prepared in examples 1, 2, 3, respectively.
Detailed Description
In order to solve the first technical problem of the present invention, the preparation method of the porous titanium copper/hydroxyapatite composite material comprises:
(1) preparing titanium copper mixed powder: uniformly mixing titanium powder and copper powder with the particle size of less than 200 meshes to obtain titanium-copper mixed powder; the blending method is preferably as follows: ball-milling and uniformly mixing by a wet method, and drying at a preferable temperature of 40-80 ℃;
(2) preparing titanium copper/hydroxyapatite mixed powder: uniformly mixing the titanium-copper mixed powder obtained in the step (1) with hydroxyapatite powder with the granularity of below 150 meshes;
(3) mixing stearic acid, a binder and mixed powder: mixing stearic acid, a binder and the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture; preferably, stearic acid and the binder are mixed firstly, and then are mixed with the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture;
(4) and (3) pressing and forming: pressing and forming the mixture obtained in the step (3) to obtain a pressed blank;
(5) and (3) vacuum sintering: sintering the pressed compact in a vacuum environment, and cooling to obtain the porous titanium copper/hydroxyapatite composite material after sintering;
wherein, the copper accounts for 5-25 wt%, the hydroxyapatite accounts for 5-30 wt%, and the titanium accounts for 45-90 wt%.
The drying in the step (1) can be carried out in a constant-temperature drying oven, the drying temperature has influence on the product performance, the drying temperature is too high, and the powder can be oxidized, generally at 40-80 ℃.
In a specific embodiment, the medium for wet ball milling in step (1) is absolute ethyl alcohol, the liquid-solid ratio of wet ball milling is preferably 1-3: 1ml/g, the grinding balls for wet ball milling are preferably stainless steel balls or hard alloy balls, the ball-material ratio of wet ball milling is preferably 5-12: 1, the ball milling time of wet ball milling is preferably 1-8 h, and the rotation speed of wet ball milling is preferably 100-300 rpm.
In a specific embodiment, the mixing time in the step (2) is 5-20 min, and the mixing is manual mixing or mechanical stirring.
In a specific embodiment, the binder in step (3) is a polyvinyl alcohol solution with a mass concentration of 2-10%, the amount of the binder is preferably 0.01-0.2 ml/g mixed powder, the mixing time is preferably 5-20 min, and the mixing in step (3) is preferably manual mixing.
In one embodiment, the particle size of the stearic acid in the step (3) is 100 to 600 μm, and the addition amount of the stearic acid is preferably 10 to 30: 90-70.
In a specific embodiment, the pressure of the molding in the step (4) is 150 to 500MPa, and the pressure maintaining time is 1 to 5 min; preferably, the green compact is then dried.
In one embodiment, the vacuum sintering process in step (5) is: the vacuum degree is kept at 10-1～10-3Pa, heating to 150-300 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 1-3 h, then heating to 400-600 ℃ at 3-10 ℃/min, preserving heat for 1-3 h, heating to 700-800 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 10-60 min, finally heating to 800-1000 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 1-3 h.
The second technical problem to be solved by the invention is to provide a novel porous titanium copper/hydroxyapatite composite material.
In order to solve the second technical problem of the invention, the porous titanium copper/hydroxyapatite composite material comprises the following components: 5-25 wt% of copper, 5-30 wt% of hydroxyapatite, 45-90 wt% of titanium and inevitable impurities.
In a specific embodiment, the porous titanium copper/hydroxyapatite composite material is prepared by the method.
In a specific embodiment, the porosity of the porous titanium copper/hydroxyapatite composite material is adjustable within 27.6-60.9%, and the preferred macropore diameter of the porous titanium copper/hydroxyapatite composite material is 100-400 μm.
In a specific embodiment, the compressive strength of the porous titanium copper/hydroxyapatite composite material is 12.9-220.0 MPa, and the elastic modulus is preferably 0.4-5.0 GPa.
The following examples are provided to further illustrate the embodiments of the present invention and are not intended to limit the scope of the present invention.
Example 1
(1) Preparing titanium copper mixed powder: weighing 50g of titanium powder with the granularity of-325 meshes and copper powder with the granularity of-400 meshes according to the mass ratio of 9:1, putting the weighed powder into a ball milling tank, adding a stainless steel grinding ball according to the ball material ratio of 10:1, adding absolute ethyl alcohol according to the proportion of 1.2mL/g of metal powder, covering the cover of the ball milling tank, carrying out ball milling on a planetary ball mill at 300 revolutions per minute for 2 hours, and drying in a constant-temperature drying box at 60 ℃ for about 10 hours to obtain titanium-copper mixed powder;
(2) preparing titanium copper/hydroxyapatite mixed powder: weighing the titanium-copper mixed powder obtained in the step (1) and hydroxyapatite powder according to a mass ratio, wherein the titanium-copper mixed powder accounts for 90%, the hydroxyapatite accounts for 10%, and manually mixing for 5min to uniformly mix the powders;
(3) mixing stearic acid, a binder and titanium copper/hydroxyapatite mixed powder: weighing stearic acid with the particle size of 300-600 mu m, adding 0.08mL of 5% polyvinyl alcohol solution into each gram of titanium copper/hydroxyapatite mixed powder, manually mixing for 5min, and then adding the titanium copper/hydroxyapatite mixed powder to ensure that the mass ratio of the stearic acid to the titanium copper/hydroxyapatite mixed powder is 10: 90, manually mixing for 5min to obtain a mixture;
(4) and (3) pressing and forming: filling the mixture obtained in the step (3) into a mold, pressing under 200MPa of uniaxial pressure and maintaining the pressure for 3min, demolding to obtain a pressed blank, putting the pressed blank into a graphite crucible, and then drying in a constant-temperature drying oven at 60 ℃ for about 8 hours;
(5) and (3) vacuum sintering: putting the pressed compact in the step (4) and the graphite crucible into a vacuum sintering furnace at 10 DEG-1～10-3And (2) heating to 200 ℃ at the temperature rise speed of 5 ℃/min under the vacuum degree of Pa, preserving heat for 1h, heating to 500 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 30min, heating to 900 ℃ at the temperature rise speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace to obtain the porous titanium copper/hydroxyapatite composite material. The porosity of the material is 27.6%, the elastic modulus is 3.4GPa, and the compressive strength is 169.7 MPa. The macroporous aperture of the porous titanium copper/hydroxyapatite composite material prepared in the embodiment 1 is 100-400 μm.
Example 2
(1) Preparing titanium copper mixed powder: weighing 50g of titanium powder with the granularity of-325 meshes and copper powder with the granularity of-400 meshes according to the mass ratio of 9:1, putting the weighed powder into a ball milling tank, adding a stainless steel grinding ball according to the ball material ratio of 10:1, adding absolute ethyl alcohol according to the proportion of 1.2mL/g of metal powder, covering the cover of the ball milling tank, carrying out ball milling on a planetary ball mill at 300 revolutions per minute for 2 hours, and drying in a constant-temperature drying box at 60 ℃ for about 10 hours to obtain titanium-copper mixed powder;
(2) preparing titanium copper/hydroxyapatite mixed powder: weighing the titanium-copper mixed powder obtained in the step (1) and hydroxyapatite powder according to a mass ratio, wherein the titanium-copper mixed powder accounts for 90%, the hydroxyapatite accounts for 10%, and manually mixing for 5min to uniformly mix the powders;
(3) mixing stearic acid, a binder and titanium copper/hydroxyapatite mixed powder: weighing stearic acid with the particle size of 300-600 mu m, adding 0.08mL of 5% polyvinyl alcohol solution into each gram of titanium copper/hydroxyapatite mixed powder, manually mixing for 5min, and then adding the titanium copper/hydroxyapatite mixed powder to enable the mass ratio of the stearic acid to the titanium copper/hydroxyapatite mixed powder to be 20: 80, manually mixing for 5min to obtain a mixture;
(4) and (3) pressing and forming: filling the mixture obtained in the step (3) into a mold, pressing under 200MPa of uniaxial pressure and maintaining the pressure for 3min, demolding to obtain a pressed blank, putting the pressed blank into a graphite crucible, and then drying in a constant-temperature drying oven at 60 ℃ for about 8 hours;
(5) and (3) vacuum sintering: putting the pressed compact in the step (4) and the graphite crucible into a vacuum sintering furnace at 10 DEG-1～10-3And (2) heating to 200 ℃ at the temperature rise speed of 5 ℃/min under the vacuum degree of Pa, preserving heat for 1h, heating to 500 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 30min, heating to 900 ℃ at the temperature rise speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace to obtain the porous titanium copper/hydroxyapatite composite material. The porosity is 46.3%, the elastic modulus is 3.0GPa, and the compressive strength is 75.5 MPa. The macroporous aperture of the porous titanium copper/hydroxyapatite composite material prepared in the embodiment 2 is 100-400 μm.
Example 3
(1) Preparing titanium copper mixed powder: weighing 50g of titanium powder with the granularity of-325 meshes and copper powder with the granularity of-400 meshes according to the mass ratio of 9:1, putting the weighed powder into a ball milling tank, adding a stainless steel grinding ball according to the ball material ratio of 10:1, adding absolute ethyl alcohol according to the proportion of 1.2mL/g of metal powder, covering the cover of the ball milling tank, carrying out ball milling on a planetary ball mill at 300 revolutions per minute for 2 hours, and drying in a constant-temperature drying box at 60 ℃ for about 10 hours to obtain titanium-copper mixed powder;
(2) preparing titanium copper/hydroxyapatite mixed powder: weighing the titanium-copper mixed powder obtained in the step (1) and hydroxyapatite powder according to a mass ratio, wherein the titanium-copper mixed powder accounts for 90%, the hydroxyapatite accounts for 10%, and manually mixing for 5min to uniformly mix the powders;
(3) mixing stearic acid, a binder and titanium copper/hydroxyapatite mixed powder: weighing stearic acid with the particle size of 300-600 mu m, adding 0.08mL of 5% polyvinyl alcohol solution into each gram of titanium copper/hydroxyapatite mixed powder, manually mixing for 5min, and adding the titanium copper/hydroxyapatite mixed powder to ensure that the mass ratio of the stearic acid to the titanium copper/hydroxyapatite mixed powder is 30: 70, manually mixing for 5min to obtain a mixture;
(4) and (3) pressing and forming: filling the mixture obtained in the step (3) into a mold, pressing under 200MPa of uniaxial pressure and maintaining the pressure for 3min, demolding to obtain a pressed blank, putting the pressed blank into a graphite crucible, and then drying in a constant-temperature drying oven at 60 ℃ for about 8 hours;
(5) and (3) vacuum sintering: putting the pressed compact in the step (4) and the graphite crucible into a vacuum sintering furnace at 10 DEG-1～10-3And (2) heating to 200 ℃ at the temperature rise speed of 5 ℃/min under the vacuum degree of Pa, preserving heat for 1h, heating to 500 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 30min, heating to 900 ℃ at the temperature rise speed of 3 ℃/min, preserving heat for 2h, and cooling to room temperature along with the furnace to obtain the porous titanium copper/hydroxyapatite composite material. The porosity is 55.1%, the elastic modulus is 1.5GPa, and the compressive strength is 36.6 MPa. The macroporous aperture of the porous titanium copper/hydroxyapatite composite material prepared in the embodiment 3 is 100-400 μm.
Example 4
(1) Preparing titanium copper mixed powder: weighing 50g of titanium powder with the granularity of-325 meshes and copper powder with the granularity of-400 meshes according to the mass ratio of 9:1, putting the weighed powder into a ball milling tank, adding a stainless steel grinding ball according to the ball material ratio of 10:1, adding absolute ethyl alcohol according to the proportion of 1.2mL/g of metal powder, covering the cover of the ball milling tank, carrying out ball milling on a planetary ball mill at 300 revolutions per minute for 2 hours, and drying in a constant-temperature drying box at 60 ℃ for about 10 hours to obtain titanium-copper mixed powder;
(2) preparing titanium copper/hydroxyapatite mixed powder: weighing the titanium-copper mixed powder obtained in the step (1) and hydroxyapatite powder according to a mass ratio, wherein the titanium-copper mixed powder accounts for 90%, the hydroxyapatite accounts for 10%, and manually mixing for 5min to uniformly mix the powders;
(3) mixing stearic acid, a binder and titanium copper/hydroxyapatite mixed powder: weighing stearic acid with the particle size of 300-600 mu m, adding 0.08mL of 5% polyvinyl alcohol solution into each gram of titanium copper/hydroxyapatite mixed powder, manually mixing for 5min, and then adding the titanium copper/hydroxyapatite mixed powder to enable the mass ratio of the stearic acid to the titanium copper/hydroxyapatite mixed powder to be 20: 80, manually mixing for 5min to obtain a mixture;
(4) and (3) pressing and forming: filling the mixture obtained in the step (3) into a mold, pressing under 200MPa of uniaxial pressure and maintaining the pressure for 3min, demolding to obtain a green compact, and processing the green compact into a blankPlacing the mixture into a graphite crucible, and then drying the mixture for about 8 hours in a constant-temperature drying oven at the temperature of 60 ℃; (5) and (3) vacuum sintering: putting the pressed compact in the step (4) and the graphite crucible into a vacuum sintering furnace at 10 DEG-1～10-3And (3) heating to 200 ℃ at the temperature rise speed of 5 ℃/min under the vacuum degree of Pa, preserving heat for 1h, heating to 500 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 2h, heating to 800 ℃ at the temperature rise speed of 5 ℃/min, preserving heat for 30min, preserving heat for 2h at 800 ℃, and cooling to room temperature along with the furnace to obtain the porous titanium copper/hydroxyapatite composite material. The porosity is 60.9%, the elastic modulus is 0.4GPa, and the compressive strength is 12.9 MPa. The macroporous aperture of the porous titanium copper/hydroxyapatite composite material prepared in the embodiment 4 is 100-400 μm.
Claims (10)
1. The preparation method of the porous titanium copper/hydroxyapatite composite material is characterized by comprising the following steps:
(1) preparing titanium copper mixed powder: uniformly mixing titanium powder and copper powder with the particle size of less than 200 meshes to obtain titanium-copper mixed powder; the blending method is preferably as follows: ball-milling and uniformly mixing by a wet method, and drying at a preferable temperature of 40-80 ℃;
(2) preparing titanium copper/hydroxyapatite mixed powder: uniformly mixing the titanium-copper mixed powder obtained in the step (1) with hydroxyapatite powder with the granularity of below 150 meshes;
(3) mixing stearic acid, a binder and mixed powder: mixing stearic acid, a binder and the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture; preferably, stearic acid and the binder are mixed firstly, and then are mixed with the titanium copper/hydroxyapatite mixed powder in the step (2) to obtain a mixture;
(4) and (3) pressing and forming: pressing and forming the mixture obtained in the step (3) to obtain a pressed blank;
(5) and (3) vacuum sintering: sintering the pressed compact in a vacuum environment, and cooling to obtain the porous titanium copper/hydroxyapatite composite material after sintering;
wherein, the copper accounts for 5-25 wt%, the hydroxyapatite accounts for 5-30 wt%, and the titanium accounts for 45-90 wt%.
2. The preparation method of the porous titanium copper/hydroxyapatite composite material according to claim 1, characterized in that in the step (1), a medium for wet ball milling is absolute ethyl alcohol, a liquid-solid ratio of the wet ball milling is preferably 1-3: 1ml/g, grinding balls for the wet ball milling are preferably stainless steel balls or hard alloy balls, a ball-material ratio of the wet ball milling is preferably 5-12: 1, a ball milling time of the wet ball milling is preferably 1-8 hours, and a rotation speed of the wet ball milling is preferably 100-300 r/min.
3. The preparation method of the porous titanium copper/hydroxyapatite composite material according to claim 1 or 2, characterized in that the mixing time in the step (2) is 5-20 min, and the mixing is manual mixing or mechanical stirring.
4. The preparation method of the porous titanium copper/hydroxyapatite composite material according to any one of claims 1 to 3, characterized in that the binder in the step (3) is a polyvinyl alcohol solution with a mass concentration of 2 to 10%, the amount of the binder is preferably 0.01 to 0.2ml/g of mixed powder, the mixing time is preferably 5 to 20min, and the mixing in the step (3) is preferably manual mixing;
the particle size of the stearic acid in the step (3) is preferably 100-600 μm, and the addition amount of the stearic acid is preferably 10-30 mass ratio of stearic acid to titanium copper/hydroxyapatite mixed powder: 90-70.
5. The method for preparing the porous titanium copper/hydroxyapatite composite material according to any one of claims 1 to 4, characterized in that the forming pressure in the step (4) is 150 to 500MPa, and the pressure holding time is 1 to 5 min; preferably, the green compact is then dried.
6. The preparation method of the porous titanium copper/hydroxyapatite composite material according to any one of claims 1 to 5, characterized in that the vacuum sintering process in the step (5) is as follows: the vacuum degree is kept at 10-1～10-3Pa, heating to 150-300 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 1-3 h, then heating to 400-600 ℃ at 3-10 ℃/min, preserving heat for 1-3 h, heating to 700-800 ℃ at a heating rate of 3-10 ℃/min, preserving heat for 10-60 min, finally heating to 800-1000 ℃ at a heating rate of 3-5 ℃/min, and preserving heat for 1-3 h.
7. The porous titanium copper/hydroxyapatite composite material is characterized by comprising the following components: 5-25 wt% of copper, 5-30 wt% of hydroxyapatite, 45-90 wt% of titanium and inevitable impurities.
8. The porous titanium copper/hydroxyapatite composite material according to claim 7, characterized in that the porous titanium copper/hydroxyapatite composite material is prepared by the method according to any one of claims 1 to 6.
9. The porous titanium copper/hydroxyapatite composite material according to claim 7 or 8, characterized in that the porosity of the porous titanium copper/hydroxyapatite composite material is adjustable from 27.6% to 60.9%, and the preferred macropore diameter of the porous titanium copper/hydroxyapatite composite material is from 100 μm to 400 μm.
10. The porous titanium copper/hydroxyapatite composite material according to any one of claims 7 to 9, characterized in that the compressive strength of the porous titanium copper/hydroxyapatite composite material is 12.9 to 220.0MPa, and the elastic modulus is preferably 0.4 to 5.0 GPa.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752813A (en) * | 2022-05-27 | 2022-07-15 | 攀枝花学院 | Medical porous Ti-Mn-Cu alloy and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251057A (en) * | 2015-10-30 | 2016-01-20 | 昆明理工大学 | Preparation method of porous titanium/hydroxyapatite composite material |
| CN105397090A (en) * | 2015-10-30 | 2016-03-16 | 昆明理工大学 | Preparation method for porous nickel titanium/hydroxyapatite composite material |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN106735185A (en) * | 2017-03-15 | 2017-05-31 | 攀枝花学院 | Gradient porous titanium and preparation method thereof |
| CN107904424A (en) * | 2017-11-09 | 2018-04-13 | 南昌航空大学 | A kind of preparation method of the medical porous Ti Cu alloys of biologically active antimicrobial form |
| CN109261968A (en) * | 2018-11-16 | 2019-01-25 | 攀枝花学院 | The preparation method of porous titanium or titanium alloy |
-
2020
- 2020-12-31 CN CN202011638050.4A patent/CN112853143A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251057A (en) * | 2015-10-30 | 2016-01-20 | 昆明理工大学 | Preparation method of porous titanium/hydroxyapatite composite material |
| CN105397090A (en) * | 2015-10-30 | 2016-03-16 | 昆明理工大学 | Preparation method for porous nickel titanium/hydroxyapatite composite material |
| CN105712735A (en) * | 2016-01-29 | 2016-06-29 | 云南省第一人民医院 | Preparation method for porous hydroxyapatite material for bone repairing |
| CN106735185A (en) * | 2017-03-15 | 2017-05-31 | 攀枝花学院 | Gradient porous titanium and preparation method thereof |
| CN107904424A (en) * | 2017-11-09 | 2018-04-13 | 南昌航空大学 | A kind of preparation method of the medical porous Ti Cu alloys of biologically active antimicrobial form |
| CN109261968A (en) * | 2018-11-16 | 2019-01-25 | 攀枝花学院 | The preparation method of porous titanium or titanium alloy |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114752813A (en) * | 2022-05-27 | 2022-07-15 | 攀枝花学院 | Medical porous Ti-Mn-Cu alloy and preparation method thereof |
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