CN111481738A - Preparation method of bioactive porous tantalum implant - Google Patents
Preparation method of bioactive porous tantalum implant Download PDFInfo
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/32—Phosphorus-containing materials, e.g. apatite
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/112—Phosphorus-containing compounds, e.g. phosphates, phosphonates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention discloses a preparation method of a bioactive porous tantalum implant, which comprises the following steps: carrying out acid washing treatment on the three-dimensional porous tantalum implantation material to obtain a pretreatment material; performing micro-arc oxidation treatment on the pretreated material to obtain an in-situ growth film layer with bioactive substances formed on the surface of the pretreated material, wherein electrolyte adopted by the micro-arc oxidation treatment comprises bioactive functional substances; and carrying out hydrothermal treatment on the in-situ growth film layer to obtain the bioactive porous tantalum implant. Experiments prove that the in-situ growth film layer can effectively endow the three-dimensional porous tantalum implant material with a bioactive function. The porous tantalum implant with living activity prepared by the invention has the advantages of simple process flow, easy realization of industrial production, simple components of electrolyte and hydrothermal treatment solution, no pollution substance, easy control and low cost, can be used for preparing various orthopedic implant materials, and has wide application prospect.
Description
Technical Field
The invention relates to the field of preparation of medical materials, in particular to a preparation method of a bioactive porous tantalum implant.
Background
At present, the processing method of porous tantalum mainly comprises a vapor deposition method, a foam impregnation method, an additive manufacturing process and the like, and porous tantalum obtained by different processes is different in form and has a good porous structure; the porous tantalum has the characteristics of no cytotoxicity, high porosity, uniform pore distribution and the like, and can be realized in the prior art, for example, a medical porous tantalum metal material (patent publication No. CN105177523A), the disclosed porous tantalum metal material has high porosity, is of a mutually communicated porous structure, has few pore dead spaces, is similar to human cancellous bone, can promote bone ingrowth, and can be applied to repair of bone wounds of multiple parts in vivo and bone defects after osteonecrosis; a porous tantalum rod and a preparation method thereof (patent publication No. CN109806032A) disclose a 3D printing porous tantalum rod, wherein the porous distribution is uniform and controllable, the compressive strength of the porous tantalum rod is 120-180 MPa, the elastic modulus is 10-20 GPa, and the porosity is 75-85%. Therefore, porous tantalum has been processed into various implant prostheses and is used clinically.
However, the surface bioactivity modification of the porous tantalum material in the prior art is not ideal. The porous tantalum prepared at present has different components with bones, cannot be chemically combined with bone formation in the early period of implantation, and has no capacity of promoting the formation of new bones. The surface biological functional modification of the three-dimensional porous tantalum has the following problems: (1) the traditional linear spraying method is difficult to uniformly spray the surface and the inside of the workpiece; (2) because of the three-dimensional porous structure, the resistance and other properties of the porous metal material are changed, and the electrochemical modification method, such as anodic oxidation and micro-arc oxidation, cannot modify the porous metal material according to the traditional electrical parameters and chemical components of the electrolyte. Therefore, surface modification of porous tantalum is an important direction of development.
Disclosure of Invention
The invention aims to provide a preparation method of a bioactive porous tantalum implant, which aims to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing a bioactive porous tantalum implant, comprising the steps of:
s1: pretreatment: carrying out acid washing treatment on the three-dimensional porous tantalum implantation material;
s2: micro-arc oxidation: immersing the pretreated three-dimensional porous tantalum implant material in electrolyte for micro-arc oxidation treatment;
s3, performing hydrothermal treatment, namely immersing the micro-arc oxidized three-dimensional porous tantalum implant material in an 8 mol/L alkaline solution at the temperature of 50-100 ℃ for 12-24 hours.
Further, comprising the steps of:
s1: pretreatment: carrying out acid washing treatment on the three-dimensional porous tantalum implant material, wherein the acid washing time is 1-5 minutes, and after the acid washing is finished, ultrasonically cleaning the three-dimensional porous tantalum implant material for 5-30 minutes by sequentially adopting acetone and deionized water, and drying the three-dimensional porous tantalum implant material for later use;
s2: micro-arc oxidation: immersing the pretreated three-dimensional porous tantalum implant material in electrolyte, performing micro-arc oxidation treatment, and generating an in-situ growth film layer on the surface of the three-dimensional porous tantalum implant material; the oxidation voltage is 200-700V, the pulse frequency is 100-1500 Hz, the peak current is set to be 10-400A, and the oxidation time is 1-30 min;
s3, performing hydrothermal treatment, namely performing ultrasonic cleaning on the micro-arc oxidized three-dimensional porous tantalum implant material by using deionized water, immersing the micro-arc oxidized three-dimensional porous tantalum implant material in 8 mol/L alkaline solution at 50-100 ℃ for 12-24 hours, and finally performing ultrasonic cleaning by using the deionized water to obtain the porous tantalum implant with bioactivity.
Further, in the step S1, the pickling solution includes 40% hydrofluoric acid, 68% nitric acid, and water, and the volume ratio of the hydrofluoric acid to the nitric acid to the water is (2-5): (8-10): (90-85).
Furthermore, in the step S2, the concentration of calcium element in the electrolyte is recorded as m mol/L, the concentration of phosphorus element is recorded as nmol/L, when m is more than or equal to 0.01 and less than 0.2, n is more than or equal to (0.1m +0.015) and less than or equal to 0.05, and when m is more than or equal to 0.2 and less than or equal to 0.8, n is more than or equal to 0.075 and less than or equal to m/0.875.
Further, the calcium source in the electrolyte is one or more of calcium acetate, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide.
Further, the phosphorus source in the electrolyte is one or more of sodium glycerophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hexametaphosphate and sodium polyphosphate.
Furthermore, the electrolyte for assisting in arc striking in the electrolyte is one of EDTA-2Na, sodium silicate, sodium hydroxide and potassium hydroxide.
Further, the pH value of the electrolyte is 11-14, and the temperature is 10-20 ℃.
Further, in step S1, the three-dimensional porous tantalum implant material is prepared by one or more of powder metallurgy, vapor deposition, and additive manufacturing.
Further, in the step S1, the three-dimensional porous tantalum implant material is one of a full porous structure and a mixed structure of a porous structure and a solid structure; the porous structure of the three-dimensional porous tantalum implantation material is one or more of an amorphous pore structure, a cubic structure, a hexagonal prism structure, a diamond structure, a rhombic dodecahedron structure and a truncated octahedron structure.
And obtaining the porous tantalum implant consisting of the three-dimensional porous tantalum implant material and the in-situ growth film layer in the surface of the three-dimensional porous tantalum implant material in an in-situ growth mode through the steps.
Furthermore, the aperture of the three-dimensional porous tantalum implantation material is 200-1500 μm, the filament diameter is 200-1000 μm, and the porosity is 30-90%.
Further, the three-dimensional porous tantalum bone implant material is a columnar structure, a columnar-like structure, a plate-like structure, a hemisphere, a block-like structure, a spherical particle, a cone or a sleeve.
Further, the three-dimensional porous tantalum implant material is an interbody fusion cage which is of a porous structure.
Further, interbody fusion cage's height is 4 ~ 15mm, and the inscribe circle diameter in structure hole is 4 ~ 10mm, and circumscribed circle diameter is 10 ~ 30mm, and upper and lower terminal surface presss from both sides angle 0 ~ 15.
Further, the three-dimensional porous tantalum implant material is an artificial vertebral body which is of a porous structure.
Further, the height of artificial centrum is 15 ~ 200mm, and the inscribe circle diameter of structure hole is 4 ~ 10mm, and circumscribed circle diameter is 8 ~ 30mm, and the upper and lower terminal surface presss from both sides angle 0 ~ 15.
Further, the three-dimensional porous tantalum implant material is an acetabulum patch, and the surface structure of the acetabulum tantalum patch is a porous structure.
Further, the three-dimensional porous tantalum implant material is an acetabular cup.
Furthermore, the spherical outer diameter of the acetabular cup is 36-72 mm, and the height of the acetabulum is 22-50 mm.
Further, the three-dimensional porous tantalum implant material is a tantalum tibial plateau, and the contact part of the tantalum tibial plateau and the tibial osteotomy surface is of a porous structure.
Further, the three-dimensional porous tantalum implant material is a columnar structure, a columnar-like structure, a plate-like structure, a hemisphere, a block-like structure, a spherical particle, a cone or a sleeve.
Further, the thickness of the in-situ growth film layer is 0.01-10 mu m, the surface of the in-situ growth film layer comprises micropores with the aperture of 0.01-2 mu m, and the porosity is 2% -25%.
Further, the thickness of the in-situ growth film layer is 0.05-5 μm.
Further, the in-situ growth film layer comprises calcium and phosphorus elements.
Has the advantages that: by applying the technical scheme of the invention, impurities and a pollution layer on the surface of the three-dimensional porous tantalum implantation material can be removed during pretreatment, the surface activation treatment effect is optimized, the surface treatment capacity of the surface and the surface in the pores of the material is improved, and the oxidation is facilitated; in order to improve the free capacity of the bioactive substances in the electrolyte as much as possible, the functional elements of the micro-arc oxidation electrolyte comprise calcium and phosphorus, the thickness of the formed in-situ growth film is easy to control under the micro-arc oxidation treatment process condition, and the proportion of the bioactive elements is relatively reasonable; in order to improve the distribution uniformity and stability of the bioactive substances in the in-situ growth film layer, the in-situ growth film layer is further subjected to hydrothermal treatment after micro-arc oxidation, calcium and phosphorus ions in the in-situ growth film layer in the hydrothermal treatment process form a hydroxyapatite structure, and the bioactive substances also migrate in the film layer, so that the porous tantalum implant with the bioactive function and a stable structure is obtained.
The in-situ growth film contains bioactive substances, so that the in-situ growth film has an osteoinduction effect. The porous tantalum implant with the bioactivity function has the advantages that the macro-aperture and the micro-aperture coexist, the micropores in the micro-arc oxidation film layer on the porous hole wall can provide anchoring points for bone growth, and meanwhile, the specific surface area of the implant material is effectively increased, so that the implant can rapidly realize bone induction and bone growth in the early stage of implantation, and the porous tantalum implant has bright application prospect on high-end orthopedic implant prostheses. Experiments prove that the in-situ growth film layer can effectively endow the three-dimensional porous tantalum implant material with a bioactive function.
The invention processes the biological inert three-dimensional porous tantalum implantation material into the porous tantalum implantation material with living activity; the process flow is simple, and the industrial production is easy to realize; the electrolyte and the hydrothermal treatment solution prepared by the method have simple components, do not contain pollutants, are easy to control and have low cost; the porous tantalum implant bioactive film layer prepared by the method is generated in situ by a porous material substrate, and has high bonding strength with the substrate; the invention can be used for preparing various orthopedic implant materials and has wide application prospect.
Drawings
FIG. 1 is a surface scanning electron micrograph of example 1;
FIG. 2 is a surface scanning electron micrograph of comparative example 1;
FIG. 3 is a surface scanning electron micrograph of comparative example 2;
FIG. 4 is an X-ray energy spectrum of example 1 of the present invention;
FIG. 5 is a scanning electron micrograph of the surface of example 1 after in vitro bioactivity test;
FIG. 6 is a scanning electron micrograph of the surface of comparative example 2 after the in vitro bioactivity test.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the preparation method of the bioactive functional porous tantalum implant comprises the following steps:
the three-dimensional porous tantalum implant material prepared by a vapor deposition method is used as a modified object of embodiment 1, the three-dimensional porous tantalum implant material is an interbody fusion cage with the height of 8mm and a porous structure, the interbody fusion cage is provided with a central hole, the diameter of an inscribed circle of the central hole is 8mm, the diameter of an circumscribed circle is 20mm, and the included angle between the upper end face and the lower end face is 8 degrees.
Example 2:
the preparation method of the bioactive functional porous tantalum implant comprises the following steps:
the three-dimensional porous tantalum implant material prepared by a powder metallurgy method is used as a modified object of embodiment 2, the three-dimensional porous tantalum implant material is an artificial cone body with the height of 50mm and a porous structure, the artificial cone body is provided with a central hole, the diameter of an inscribed circle of the central hole is 6mm, the diameter of an circumscribed circle is 20mm, and the included angle between the upper end face and the lower end face is 8 degrees, the artificial cone body is subjected to acid cleaning treatment, the adopted acid cleaning solution comprises hydrofluoric acid, nitric acid and water, the concentration of the hydrofluoric acid is 40%, the concentration of the nitric acid is 68%, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 2: 8: 90, the acid cleaning time is 2 minutes, the acid cleaned artificial cone body is sequentially subjected to ultrasonic cleaning by using acetone and deionized water for 5 minutes, after the ultrasonic cleaning, the artificial cone body is subjected to micro-arc oxidation treatment by ultrasonic cleaning, the electrolyte comprises calcium and phosphorus elements, the calcium source is calcium citrate, the phosphorus source is disodium hydrogen phosphate and sodium hexametaphosphate, the electrolyte for assisting in arc generation is potassium hydroxide, the pH value is 11, the electrolyte is 10 ℃, the oxidation voltage is 200V, the pulse frequency is 120Hz, the peak current is set to be 15A, the oxidation time is set to 1min, the electrolyte after the micro-arc oxidation, the ultrasonic cleaning is used for immersing the artificial cone body in the artificial cone body after the ultrasonic.
Example 3:
the preparation method of the bioactive functional porous tantalum implant comprises the following steps:
the three-dimensional porous tantalum implant material prepared by using an electron beam melting technology is used as a modified object of embodiment 3, the three-dimensional porous tantalum implant material is an acetabulum cup, the surface structure of the acetabulum cup is a porous structure, the spherical outer diameter of the acetabulum cup is 50mm, the height of an acetabulum is 36mm, the acetabulum cup is subjected to acid cleaning treatment, the adopted acid cleaning solution comprises hydrofluoric acid, nitric acid and water, the concentration of the hydrofluoric acid is 40%, the concentration of the nitric acid is 68%, the volume ratio of the hydrofluoric acid to the nitric acid to the water is 5: 10: 85, the acid cleaning time is 5 minutes, the acetabulum cup after acid cleaning is subjected to ultrasonic cleaning by using acetone and deionized water for 30 minutes in sequence, after ultrasonic cleaning, the acetabulum cup is subjected to micro-arc oxidation treatment, the electrolyte comprises calcium and phosphorus elements, the calcium phosphate source is monocalcium phosphate, the electrolyte for assisting in arc striking is EDTA-2Na, the pH value of the electrolyte is 14, the electrolyte is 20 ℃, the oxidation voltage is 700V, the pulse frequency is 1500Hz, the peak current is set to 400A, the oxidation time is 30 minutes, the acetabulum cup after oxidation is subjected to ultrasonic vibration treatment by using the micro-arc ultrasonic vibration, and then the acetabulum cup is immersed in the ultrasonic.
Comparative example 1:
the preparation method of the porous tantalum implant without hydrothermal treatment comprises the following steps:
the intervertebral cage of example 1 was used as a modified object of comparative example 1. Carrying out acid pickling treatment on the interbody fusion cage, wherein the adopted acid pickling solution comprises hydrofluoric acid, nitric acid and water; the concentration of hydrofluoric acid is 40%, the concentration of nitric acid is 68%, and the volume ratio of hydrofluoric acid, nitric acid and water is 5: 8: 87; the acid washing time was 3 minutes. Ultrasonically cleaning the intervertebral fusion cage implant material subjected to acid cleaning by sequentially adopting acetone and deionized water for 19min, and after ultrasonic cleaning, performing micro-arc oxidation treatment on the intervertebral fusion cage, wherein the electrolyte comprises calcium and phosphorus elements, and the calcium source comprises calcium acetate, calcium dihydrogen phosphate and calcium glycerophosphate; the phosphorus source is sodium glycerophosphate. The electrolyte for assisting the arcing is sodium silicate, the pH value of the electrolyte is 12, and the temperature of the electrolyte is 10-20 ℃. The oxidation voltage was 550V, the pulse frequency was 900Hz, the peak current was set at 220A, and the oxidation time was 20min, resulting in a porous tantalum implant.
Comparative example 2: commercially available conventional porous tantalum implants were taken without any treatment.
Experiment 1:
the surfaces of the porous tantalum implants obtained in the example 1 and the comparative examples 1-2 are subjected to electron microscope scanning, and the obtained surface scanning electron microscope images are shown in the attached drawings 1-3 of the specification:
as can be seen from fig. 1: the pore size of the micropores of the in-situ growth film layer on the surface of the porous tantalum implant obtained in the embodiment 1 is 0.01-2 mu m, the porosity is about 15%, and after hydrothermal treatment, the surface of the porous tantalum implant is provided with an activated deposition layer; as can be seen from fig. 2: the surface of the porous tantalum implant which is not subjected to hydrothermal treatment and is obtained in the comparative example 1 only has a porous layer subjected to oxidation treatment, and an activated layer does not appear; the surface topography of the porous tantalum implant obtained in comparative example 2 is shown in fig. 3, which is a metal surface.
Experiment 2:
the bioactive porous tantalum implants obtained in the examples 1 to 3 are detected, wherein the element compositions of the in-situ growth film layers of the examples 1 to 5 are detected by adopting an X-ray energy spectrum, the X-ray energy spectrum of the example 1 is shown in a figure 4, and the element contents of the porous tantalum implants of the examples 1 to 3 are shown in a table 1.
TABLE 1 porous tantalum implants obtained in examples 1-3 have the respective element contents (atomic percent)
| Ca | P | Ta | O | |
| Example 1 | 6.89 | 2.75 | 20.37 | 71.97 |
| Example 2 | 7.01 | 2.55 | 19.96 | 70.53 |
| Examples3 | 7.14 | 2.87 | 20.03 | 71.38 |
According to the data in fig. 2 and table 1, it can be seen that the intervertebral cage, the artificial vertebral body and the acetabular cup provided in the embodiments 1 to 3, through the technical scheme of the present invention, have the surfaces attached with bioactive substances such as Ga/P, etc., to achieve the purpose of surface modification.
Experiment 3:
the in vitro bioactivity test was performed according to "in vitro evaluation of apatite formation capability of YY/T1447-2016 surgical implant materials". In vitro activity experiments 1.5 times Simulated Body Fluid (SBF) was used as the soak solution. The porous tantalum implants obtained in example 1 and comparative example 2 were subjected to a soaking experiment in a 37 ℃ constant temperature water bath for 14 days, the SBF solution was replaced every two days during the soaking experiment, and after one week, when the simulated body fluid became turbid, the fluid replacement time was changed to once a day. And after the soaking experiment is finished, taking out a porous tantalum implant sample, cleaning the porous tantalum implant sample by using deionized water, drying the porous tantalum implant sample in a drying box, and observing the porous tantalum implant sample by using a scanning electron microscope to observe the condition of hydroxyapatite deposited on the surface of the porous tantalum implant sample.
According to the test results of in vitro activity assay analysis, it can be known that: as shown in fig. 5, a large amount of hydroxyapatite was deposited on the surface of the porous tantalum implant obtained in example 1, indicating that the bioactive functional porous tantalum implant material can achieve osteoinduction and bone ingrowth; as shown in fig. 6, hydroxyapatite is not deposited on the surface of the porous tantalum implant obtained in comparative example 2, and the bioactivity is poor.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof; it is also possible to implement other implementation variants by means of combinations of the means and features mentioned in the invention, without leaving the scope of the invention. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (10)
1. A preparation method of a bioactive porous tantalum implant is characterized by comprising the following steps: the method comprises the following steps:
s1: pretreatment: carrying out acid washing treatment on the three-dimensional porous tantalum implantation material;
s2: micro-arc oxidation: immersing the pretreated three-dimensional porous tantalum implant material in electrolyte for micro-arc oxidation treatment;
s3, performing hydrothermal treatment, namely immersing the micro-arc oxidized three-dimensional porous tantalum implant material in an 8 mol/L alkaline solution at the temperature of 50-100 ℃ for 12-24 hours.
2. The method of claim 1, wherein the porous tantalum implant is prepared by: the method comprises the following steps:
s1: pretreatment: carrying out acid washing treatment on the three-dimensional porous tantalum implant material, wherein the acid washing time is 1-5 minutes, and after the acid washing is finished, ultrasonically cleaning the three-dimensional porous tantalum implant material for 5-30 minutes by sequentially adopting acetone and deionized water, and drying the three-dimensional porous tantalum implant material for later use;
s2: micro-arc oxidation: immersing the pretreated three-dimensional porous tantalum implant material in electrolyte, performing micro-arc oxidation treatment, and generating an in-situ growth film layer on the surface of the three-dimensional porous tantalum implant material; the oxidation voltage is 200-700V, the pulse frequency is 100-1500 Hz, the peak current is set to be 10-400A, and the oxidation time is 1-30 min;
s3, performing hydrothermal treatment, namely performing ultrasonic cleaning on the micro-arc oxidized three-dimensional porous tantalum implant material by using deionized water, immersing the micro-arc oxidized three-dimensional porous tantalum implant material in 8 mol/L alkaline solution at 50-100 ℃ for 12-24 hours, and finally performing ultrasonic cleaning by using the deionized water to obtain the porous tantalum implant with bioactivity.
3. The method of claim 1, wherein the porous tantalum implant is prepared by: in the step S1, the pickling solution comprises 40% hydrofluoric acid, 68% nitric acid and water, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is (2-5): (8-10): (90-85).
4. The method for preparing a bioactive porous tantalum implant according to claim 1, wherein in the step S2, the concentration of calcium element in the electrolyte is represented as mmol/L, the concentration of phosphorus element is represented as n mol/L, when m is more than or equal to 0.01 and less than 0.2, n is more than or equal to 0.1m +0.015 and less than or equal to 0.05, and when m is more than or equal to 0.2 and less than or equal to 0.8, n is more than or equal to 0.075 and less than or equal to m/0.875.
5. The method for preparing a bioactive porous tantalum implant according to claim 4, wherein: the calcium source in the electrolyte is one or more of calcium acetate, calcium dihydrogen phosphate, calcium glycerophosphate, calcium citrate, calcium lactate and calcium oxide.
6. The method for preparing a bioactive porous tantalum implant according to claim 4, wherein: the phosphorus source in the electrolyte is one or more of sodium glycerophosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium hexametaphosphate and sodium polyphosphate.
7. The method for preparing a bioactive porous tantalum implant according to claim 4, wherein: the electrolyte for assisting in arcing in the electrolyte is one of EDTA-2Na, sodium silicate, sodium hydroxide and potassium hydroxide.
8. The method for preparing a bioactive porous tantalum implant according to claim 4, wherein: the pH value of the electrolyte is 11-14, and the temperature is 10-20 ℃.
9. The method of claim 1, wherein the porous tantalum implant is prepared by: in the step S1, the three-dimensional porous tantalum implant material is prepared by one or more of powder metallurgy, vapor deposition, and additive manufacturing techniques.
10. The method of claim 1, wherein the porous tantalum implant is prepared by: in the step S1, the three-dimensional porous tantalum implant material is one of a full porous structure and a mixed structure of porous and solid structures; the porous structure of the three-dimensional porous tantalum implantation material is one or more of an amorphous pore structure, a cubic structure, a hexagonal prism structure, a diamond structure, a rhombic dodecahedron structure and a truncated octahedron structure.
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