CN111888054A - Titanium alloy implant with micro-nano composite structure and preparation method thereof - Google Patents
Titanium alloy implant with micro-nano composite structure and preparation method thereof Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 66
- 239000007943 implant Substances 0.000 title claims abstract description 54
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 15
- 238000005530 etching Methods 0.000 claims abstract description 15
- 238000004140 cleaning Methods 0.000 claims description 33
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000003754 machining Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 210000000988 bone and bone Anatomy 0.000 abstract description 14
- 210000000963 osteoblast Anatomy 0.000 abstract description 6
- 230000012010 growth Effects 0.000 abstract description 5
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- 238000003672 processing method Methods 0.000 abstract description 3
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- 239000002086 nanomaterial Substances 0.000 description 8
- 230000004069 differentiation Effects 0.000 description 5
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 238000005488 sandblasting Methods 0.000 description 3
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
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- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 238000011160 research Methods 0.000 description 2
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- 238000010521 absorption reaction Methods 0.000 description 1
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- 238000002715 modification method Methods 0.000 description 1
- 235000001968 nicotinic acid Nutrition 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 210000002997 osteoclast Anatomy 0.000 description 1
- 210000004409 osteocyte Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
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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
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
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- A61F2/3094—Designing or manufacturing processes
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2/30771—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth applied in original prostheses, e.g. holes or grooves
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- A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
- A61F2/02—Prostheses implantable into the body
- A61F2/30—Joints
- A61F2/30767—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth
- A61F2002/3093—Special external or bone-contacting surface, e.g. coating for improving bone ingrowth for promoting ingrowth of bone tissue
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- A—HUMAN NECESSITIES
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- A61F2310/00—Prostheses classified in A61F2/28 or A61F2/30 - A61F2/44 being constructed from or coated with a particular material
- A61F2310/00005—The prosthesis being constructed from a particular material
- A61F2310/00011—Metals or alloys
- A61F2310/00023—Titanium or titanium-based alloys, e.g. Ti-Ni alloys
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- A—HUMAN NECESSITIES
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- A61L2430/00—Materials or treatment for tissue regeneration
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- A—HUMAN NECESSITIES
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/12—Materials or treatment for tissue regeneration for dental implants or prostheses
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- Health & Medical Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Vascular Medicine (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Heart & Thoracic Surgery (AREA)
- Epidemiology (AREA)
- Cardiology (AREA)
- Biomedical Technology (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Surgery (AREA)
- Dermatology (AREA)
- Medicinal Chemistry (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- ing And Chemical Polishing (AREA)
- Dental Prosthetics (AREA)
- Prostheses (AREA)
Abstract
The invention discloses a titanium alloy implant with a micro-nano composite structure, wherein a plurality of micron-sized micro grooves are arranged on a titanium alloy body, the size, the shape and the precision of the micro grooves can be controlled, and the regular micro groove structure can control the oriented growth of osteoblasts, so that the implant is firmly combined with bone tissues, and the stability of the implant is improved. The invention also provides a method for preparing the titanium alloy implant with the micro-nano composite structure, which adopts a processing method of multiple acid etching after processing, the structure is directly converted from the titanium alloy material, no obvious interface exists between the titanium alloy material and a substrate, the surface structure is uniform, and the method is different from the preparation methods of spraying, sintering and the like from inside to outside in the prior art.
Description
Technical Field
The invention relates to the technical field of medical implant processing, in particular to a titanium alloy implant with a micro-nano composite structure and a preparation method thereof.
Background
Medical biological titanium and its alloy have excellent comprehensive performance, such as low elastic modulus, low density, high specific strength, good corrosion resistance, good biocompatibility, high fatigue strength, no toxicity and harm to human body, etc., and are widely used in medicine, mainly used as orthopedic internal fixation implant, hard tissue replacement implant (artificial bone, artificial joint and dental implant) and heart and cardiovascular implant, and have good clinical use effect. However, titanium and its alloy are biologically inert materials, and the titanium alloy implant has poor binding ability with human body, is difficult to form new bone, and has long healing time. In addition, because the elastic modulus of the titanium alloy is higher than that of the bone, the titanium implant and the bone are in mechanical embedded combination rather than stable biochemical combination, and stress shielding exists between the implant and the bone, so that the implant is loosened and even falls off. How to improve the biocompatibility of the titanium alloy and improve the osseointegration capability becomes one of the research hotspots of titanium alloy implants.
From the viewpoint of bionics, an ideal bone implant should have a micro-nano-scale structure, which is more beneficial to the realization of the functions of cells, and an appropriate micro-scale structure can increase the contact area between the implant and the bone, improve the success rate of implantation surgery, and the nano-scale structure has interaction with protein and cell membrane receptors, thereby promoting cell differentiation and tissue regeneration. In various micro-nano composite structures, researches show that in a regular surface microstructure, a surface with a regular micro-pattern can induce the oriented growth of osteocytes, and can generate certain influence on the proliferation and differentiation of the cells. The implant with the micro-nano structure on the surface increases the combination area of the implant and human tissues, shows higher biocompatibility, and has more positive effects on adhesion, proliferation, differentiation and the like of human cells when the micro-nano structure on the surface is more regular.
In order to obtain a micro-nano structure with good biocompatibility, various surface modification methods are used for treating a titanium implant so as to obtain good biocompatibility, such as thermal spraying, physical vapor deposition, ion implantation and deposition, sand blasting, laser processing and the like, but the existing methods have many problems, such as that residual particles after sand blasting can cause adverse effects on osseointegration; the titanium alloy surface processed by laser has a large amount of slag residues and is difficult to clean; the pit edge constructed by sand blasting and acid etching is relatively sharp and has a certain difference with an absorption pit formed by osteoclast. The most important problem is that the titanium alloy surface treated by the methods can not obtain a regular micro-nano structure, the irregular micro-nano composite structure reasonably controls the oriented growth, proliferation and differentiation of osteoblasts, and the biocompatibility effect expressed by the irregular micro-nano composite structure is poor compared with that expressed by the regular micro-nano composite structure.
Therefore, how to change the decrease of biocompatibility caused by the irregularity of the micro-nano structure on the surface of the titanium alloy implant in the prior art becomes a problem to be solved by those skilled in the art.
Disclosure of Invention
The invention aims to provide a titanium alloy implant with a micro-nano composite structure and a preparation method thereof, which are used for solving the problems in the prior art, so that the titanium alloy implant with the micro-nano composite structure is easier to integrate with bone tissues, and the stability of the implant is improved.
In order to achieve the purpose, the invention provides the following scheme: the invention provides a titanium alloy implant with a micro-nano composite structure, which comprises a titanium alloy body, wherein a plurality of micro grooves arranged side by side are formed in the titanium alloy body, the depth of each micro groove is 8-10 mu m, the width of each micro groove is 10-20 mu m, ridge structures are arranged on the side walls and the bottom of the micro grooves, the width of each ridge structure is 0.5-2 mu m, a plurality of pits are formed in the inner walls of the micro grooves and the surfaces of the ridge structures, and the diameter of each pit is 10-20 nm.
Preferably, the cross section of each micro groove is V-shaped, and the included angle between every two adjacent micro grooves is 50-60 degrees.
Preferably, the surface roughness of the micro-groove is 200-300 nm.
The invention also provides a method for preparing the titanium alloy implant with the micro-nano composite structure, which comprises the following steps:
step one, polishing and rough machining are carried out on a titanium alloy material, and cleaning and drying are carried out;
step two, carrying out micron-grade cutting processing on the titanium alloy material after rough processing on an ultraprecise machine processing machine tool to obtain a micro-groove structure, and cleaning and drying the micro-groove structure;
and step three, sequentially putting the titanium alloy material subjected to the ultraprecision machining into a mixed solution of hydrofluoric acid and nitric acid, a mixed solution of hydrochloric acid and sulfuric acid and a mixed solution of concentrated sulfuric acid and hydrogen peroxide for acid etching, and cleaning and drying the titanium alloy material subjected to the acid etching.
Preferably, in the step one, rough machining is performed by adopting a three-axis numerical control machine tool, and the machining parameters are set as follows: the spindle speed is 500r/min, the feed rate is 0.1mm/r, the cutting depth is 0.2mm, and a hard alloy cutter is used.
Preferably, in the second step, the superfinishing machine tool is an ultraprecise free-form surface machine tool, the tool is a natural diamond tool, the arc radius of the tool tip is 0.02mm, the tool is machined in a mode that a main shaft keeps not rotating and the tool moves in the machining process, and the micro groove is obtained after machining.
Preferably, in the third step, the titanium alloy material after being subjected to the ultra-precision processing is put into a mixed solution of hydrofluoric acid with the concentration of 0.53mol/L and nitric acid with the concentration of 0.29mol/L, treated for 5min at room temperature, and washed clean by a large amount of clear water; then acid etching is carried out for 60min at 80 ℃ by using a mixed solution of hydrochloric acid with the concentration of 1.0mol/L and sulfuric acid with the concentration of 1.5 mol/L; and finally, treating for 30min by using a mixed solution of concentrated sulfuric acid and 30% hydrogen peroxide at room temperature.
Preferably, in the first step and the second step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is carried out for three times, the cleaning solution adopted in the three times of cleaning is acetone, ethanol and deionized water in sequence, and the cleaning time of each time is not more than 10 min; in the third step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is only carried out once, and the cleaning solution is deionized water.
Compared with the prior art, the invention has the following technical effects: according to the titanium alloy implant with the micro-nano composite structure, the plurality of micron-sized micro grooves are formed in the titanium alloy body, the size, the shape and the precision of the micro grooves can be controlled, the regular micro groove structure can control the oriented growth of osteoblasts, the implant and bone tissues are firmly combined, and the stability of the implant is improved. The invention also provides a method for preparing the titanium alloy implant with the micro-nano composite structure, which adopts a processing method of multiple acid etching after processing, the structure is directly converted from the titanium alloy material, no obvious interface exists between the titanium alloy material and a substrate, the surface structure of the substrate is uniform, and the method is different from the preparation methods of spraying, sintering and the like from inside to outside in the prior art.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic sectional structure view of a titanium alloy implant with a micro-nano composite structure according to the present invention;
wherein 1 is a micro groove, h is the depth of the micro groove, b is the width of the micro groove, and alpha is the included angle between adjacent micro grooves.
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.
The invention aims to provide a titanium alloy implant with a micro-nano composite structure and a preparation method thereof, which are used for solving the problems in the prior art, so that the titanium alloy implant with the micro-nano composite structure is easier to integrate with bone tissues, and the stability of the implant is improved.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1, fig. 1 is a schematic structural diagram of a titanium alloy implant with a micro-nano composite structure according to the present invention.
The invention provides a titanium alloy implant with a micro-nano composite structure, which comprises a titanium alloy body, wherein a plurality of micro grooves 1 which are arranged side by side are formed in the titanium alloy body, the depth of each micro groove 1 is 8-10 mu m, and the width of each micro groove 1 is 10-20 mu m.
According to the titanium alloy implant with the micro-nano composite structure, the plurality of micron-sized micro grooves 1 are formed in the titanium alloy body, the size of each micro groove 1 can be controlled, and the regular structure of each micro groove 1 can control the oriented growth of osteoblasts, so that the implant is firmly combined with bone tissues, and the stability of the implant is improved.
The cross section of each micro groove 1 is V-shaped, the included angle between every two adjacent micro grooves 1 is 50-60 degrees, and the processing difficulty is reduced.
In addition, it is emphasized that the side walls and the bottom of the micro-groove 1 have ridge structures, the ridge structures are orderly arranged, and the width of the ridge structures is 0.5-2 μm.
Specifically, the inner wall of the micro groove 1 and the surface of the ridge structure are provided with a plurality of pits, the pits are distributed on the surfaces of the micro groove 1 and the ridge structure, the diameter of each pit is 10-20nm, and the nano-scale pits can provide a climbing space for pseudo feet of cells, are firmly combined with bone tissues and improve the stability of the implant.
More specifically, the surface roughness of the micro-groove 1 is 200-300nm, and hydroxyapatite is induced to form after multiple acid etching treatment, so that the adhesion, proliferation and differentiation of osteoblasts are enhanced.
The invention also provides a method for preparing the titanium alloy implant with the micro-nano composite structure, which comprises the following steps:
step one, carrying out rough machining on a titanium alloy material, cleaning and drying;
step two, carrying out micron-scale cutting processing on the titanium alloy material after rough processing on an ultraprecise machine processing machine tool to obtain a micro-groove 1 array structure, and cleaning and drying the micro-groove 1 array structure;
and step three, sequentially putting the ultraprecisely processed titanium alloy sample into a mixed solution of hydrofluoric acid and nitric acid, a mixed solution of hydrochloric acid and sulfuric acid, and a mixed solution of concentrated sulfuric acid and hydrogen peroxide for acid etching processing to obtain a ridge-shaped structure and a pit, and cleaning and drying the ridge-shaped structure and the pit after the acid etching processing.
The method for preparing the titanium alloy implant with the micro-nano composite structure adopts a processing method of multiple acid etching after processing, the structure is directly converted from a titanium alloy material, no obvious interface exists between the titanium alloy material and a substrate, the surface structure is uniform, and the method is different from the preparation methods of spraying, sintering and the like from inside to outside in the prior art, the surface of the implant provided by the invention is provided with micro grooves 1, and the combination degree of a surface structure layer and a bone tissue is higher.
In the present embodiment, the titanium alloy sample is medical titanium alloy Ti6Al4V, and the total surface area is about 500mm2In the first step, the machine tool used for rough machining is a three-axis numerical control machine tool, the rotating speed of a main shaft is 500r/min, the feed rate is 0.1mm/r, the cutting depth is 0.2mm, and the cutter is a hard alloy cutter.
And in the second step, an ultraprecise free-form surface processing machine tool is adopted, the specific machine tool equipment used is a U.S. ultraprecise free-form surface processing machine tool Moore Nanotech 350FG, the cutter is a natural diamond cutter, the arc radius of the tool nose is 0.02mm, the machining process is carried out in a mode that a main shaft does not rotate and the cutter moves, and the micro groove 1 is obtained after machining.
In the third step, the titanium alloy sample after the ultraprecise processing is put into a mixed solution of hydrofluoric acid with the concentration of 0.53mol/L and nitric acid with the concentration of 0.29mol/L, treated for 5min at room temperature, and washed clean by a large amount of clear water; then acid etching is carried out for 60min at 80 ℃ by using a mixed solution of hydrochloric acid with the concentration of 1.0mol/L and sulfuric acid with the concentration of 1.5 mol/L; and finally, treating for 30min by using a mixed solution of concentrated sulfuric acid and 30% hydrogen peroxide at room temperature.
In the first step and the second step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is carried out for three times, the cleaning solution adopted in the three-time cleaning is acetone, ethanol and deionized water in sequence, and the cleaning time is not more than 10min each time; in the third step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is only carried out once, and the cleaning solution is deionized water.
The titanium alloy implant with the micro-nano composite structure prepared by the preparation method of the invention is subjected to amplification observation under a scanning electron microscope, and the appearance of the micro-nano structure can be seen as follows: the width of the micro-groove 1 is 10-20 μm, the depth of the micro-groove 1 is 8-10 μm, the inner wall and the bottom of the micro-groove 1 generate a micron-scale ordered ridge structure, the width of the micro-groove 1 is 0.5-2 μm, nano-scale pits are covered on the micro-groove 1 and the ridge structure, the depth and the size of the pits are different, and the diameter of the pits is 10-20 nm. The titanium alloy implant with the micro-nano composite structure disclosed by the invention is subjected to multiple acid etching treatment to induce hydroxyapatite to form, so that the adhesion, proliferation and differentiation of osteoblasts are enhanced.
The principle and the implementation mode of the invention are explained by applying a specific example, and the description of the embodiment is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In summary, this summary should not be construed to limit the present invention.
Claims (8)
1. A titanium alloy implant with a micro-nano composite structure is characterized in that: the titanium alloy body is provided with a plurality of micro grooves arranged side by side, the depth of each micro groove is 8-10 mu m, the width of each micro groove is 10-20 mu m, the side wall and the bottom of each micro groove are provided with ridge-shaped structures, the width of each ridge-shaped structure is 0.5-2 mu m, a plurality of pits are formed in the inner wall of each micro groove and the surface of each ridge-shaped structure, and the diameter of each pit is 10-20 nm.
2. The titanium alloy implant with the micro-nano composite structure according to claim 1, wherein: the cross section of each micro groove is V-shaped, and the included angle between every two adjacent micro grooves is 50-60 degrees.
3. The titanium alloy implant with the micro-nano composite structure according to claim 2, wherein: the surface roughness of the micro-groove is 200-300 nm.
4. A method for preparing the titanium alloy implant with the micro-nano composite structure according to any one of claims 1 to 3, is characterized by comprising the following steps:
step one, carrying out rough machining on a titanium alloy material, cleaning and drying;
step two, carrying out micron-grade cutting processing on the titanium alloy material after rough processing on an ultraprecise machine processing machine tool to obtain a micro-groove structure, and cleaning and drying the micro-groove structure;
and step three, sequentially putting the titanium alloy material subjected to the ultraprecision machining into a mixed solution of hydrofluoric acid and nitric acid, a mixed solution of hydrochloric acid and sulfuric acid and a mixed solution of concentrated sulfuric acid and hydrogen peroxide for acid etching, and cleaning and drying the titanium alloy material subjected to the acid etching.
5. The method for preparing the titanium alloy implant with the micro-nano composite structure according to claim 4, wherein the method comprises the following steps: in the first step, a three-axis numerical control machine tool is adopted for rough machining, and machining parameters are set as follows: the spindle speed is 500r/min, the feed rate is 0.1mm/r, the cutting depth is 0.2mm, and a hard alloy cutter is used.
6. The method for preparing the titanium alloy implant with the micro-nano composite structure according to claim 4, wherein the method comprises the following steps: and in the second step, the superfinishing machine tool adopts an ultraprecise free-form surface machine tool, the cutter is a natural diamond cutter, the arc radius of the tool tip is 0.02mm, the main shaft is kept to be not rotated, the cutter moves in the machining process, and the micro groove is obtained after machining.
7. The method for preparing the titanium alloy implant with the micro-nano composite structure according to claim 4, wherein the method comprises the following steps: in the third step, the titanium alloy material after the ultraprecise processing is put into a mixed solution of hydrofluoric acid with the concentration of 0.53mol/L and nitric acid with the concentration of 0.29mol/L, treated for 5min at room temperature, and washed clean by a large amount of clear water; then acid etching is carried out for 60min at 80 ℃ by using a mixed solution of hydrochloric acid with the concentration of 1.0mol/L and sulfuric acid with the concentration of 1.5 mol/L; and finally, treating for 30min by using a mixed solution of concentrated sulfuric acid and 30% hydrogen peroxide at room temperature.
8. The method for preparing the titanium alloy implant with the micro-nano composite structure according to claim 4, wherein the method comprises the following steps: in the first step and the second step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is carried out for three times, the cleaning solution adopted in the three-time cleaning is acetone, ethanol and deionized water in sequence, and the cleaning time is not more than 10min each time; in the third step, an ultrasonic cleaning mode is adopted during cleaning, the cleaning is only carried out once, and the cleaning solution is deionized water.
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