CN115055697A - Preparation method of super-hydrophilic micro-nano surface of nickel-titanium implant for 3D printing - Google Patents
Preparation method of super-hydrophilic micro-nano surface of nickel-titanium implant for 3D printing Download PDFInfo
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- CN115055697A CN115055697A CN202210646286.5A CN202210646286A CN115055697A CN 115055697 A CN115055697 A CN 115055697A CN 202210646286 A CN202210646286 A CN 202210646286A CN 115055697 A CN115055697 A CN 115055697A
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- 239000007943 implant Substances 0.000 title claims abstract description 166
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910001000 nickel titanium Inorganic materials 0.000 title claims abstract description 114
- 238000010146 3D printing Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012153 distilled water Substances 0.000 claims abstract description 46
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 42
- 230000003647 oxidation Effects 0.000 claims abstract description 37
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 28
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000004381 surface treatment Methods 0.000 claims abstract description 23
- 238000005488 sandblasting Methods 0.000 claims abstract description 21
- 239000011259 mixed solution Substances 0.000 claims abstract description 20
- LWMHPOLRJIRLPN-UHFFFAOYSA-N 6-pyridin-2-ylpyridine-3-carboxylic acid Chemical compound N1=CC(C(=O)O)=CC=C1C1=CC=CC=N1 LWMHPOLRJIRLPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001639 calcium acetate Substances 0.000 claims abstract description 12
- 229960005147 calcium acetate Drugs 0.000 claims abstract description 12
- 235000011092 calcium acetate Nutrition 0.000 claims abstract description 12
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000005498 polishing Methods 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 5
- 238000005530 etching Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims description 20
- 229910052593 corundum Inorganic materials 0.000 claims description 13
- 239000010431 corundum Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 5
- 238000000861 blow drying Methods 0.000 claims description 4
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 abstract description 28
- 239000002114 nanocomposite Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 12
- 210000000988 bone and bone Anatomy 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000012567 medical material Substances 0.000 abstract description 2
- 239000002253 acid Substances 0.000 description 11
- 239000002135 nanosheet Substances 0.000 description 10
- 238000005507 spraying Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 229910001069 Ti alloy Inorganic materials 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- 230000006872 improvement Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 210000001519 tissue Anatomy 0.000 description 2
- 206010067484 Adverse reaction Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006838 adverse reaction Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000024245 cell differentiation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/62—Treatment of workpieces or articles after build-up by chemical means
-
- 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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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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
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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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
- 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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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
- B22F10/60—Treatment of workpieces or articles after build-up
- B22F10/66—Treatment of workpieces or articles after build-up by mechanical means
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
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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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/26—Acidic compositions for etching refractory metals
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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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/32—Alkaline compositions
- C23F1/38—Alkaline compositions for etching refractory metals
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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
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- A61L2400/00—Materials characterised by their function or physical properties
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- A61L2400/16—Materials with shape-memory or superelastic properties
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- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
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Abstract
The invention relates to the technical field of medical material manufacturing, in particular to a method for preparing a super-hydrophilic micro-nano surface of a 3D printing nickel-titanium implant, which comprises the following steps: polishing and sand blasting the surface of the 3D printed nickel-titanium implant; ultrasonically cleaning distilled water, acetone, absolute ethyl alcohol and distilled water respectively, treating by using a mixed solution of hydrofluoric acid and nitric acid, placing the 3D printing nickel-titanium implant into a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, and then performing oxidation surface treatment by adopting voltage electrolysis; and (3) performing alkaline etching treatment on the surface of the oxidized 3D printed nickel-titanium implant by using a sodium hydroxide solution, so that a coarse porous micron structure with different pore diameters is formed on the surface of the implant, the recognition degree with human bones is improved, a micro-nano composite structure is endowed to the implant, and the surface of the implant has super-hydrophilicity.
Description
Technical Field
The invention relates to the technical field of medical material manufacturing, in particular to a preparation method of a super-hydrophilic micro-nano surface of a 3D printing nickel-titanium implant.
Background
Among biomedical metal materials, titanium and titanium alloys are nontoxic, lightweight, high in specific strength and the Young's modulus is closest to that of human bones, and have gradually become the preferred materials for repair and replacement of human hard tissues. Although titanium alloy is the most ideal medical metal material at present in theory, the actual clinical application effect is not satisfactory. Firstly, titanium and titanium alloys have low surface hardness and poor wear resistance, and can generate severe wear in the friction process, and meanwhile, nickel elements in the alloys can enter human bodies in an ion form due to the corrosion action of human body fluids, so that adverse reactions are caused. In addition, after the titanium and the titanium alloy are implanted into a human body, the titanium and the titanium alloy are only mechanically combined with a growing bone, so that firm chemical combination cannot be formed, and bioactivity is lacked. Therefore, good biological activity, wear resistance and corrosion resistance are the main concerns in the clinical application process of the medical titanium and titanium alloy at present.
Nickel titanium shape memory alloys are widely used in the biomedical field due to their unique shape memory properties, superelasticity, good biocompatibility, etc. With the development of 3D printing technology, it has become possible to construct complex structures and to customize medical implants individually. As a medical implant material, the surface properties such as morphology, roughness, hydrophilicity and the like of the medical implant material can influence the proliferation, adhesion and differentiation of cells on the surface of the medical implant material, and further have important influence on the compatibility with tissues after implantation, long-term biosafety and the like. Therefore, an ideal 3D printing nickel-titanium implant surface is constructed, so that the surface has higher bioactivity, side reactions are reduced, and a stable implantation effect is obtained, which is a development target of the existing 3D printing nickel-titanium implant, so that a preparation method of a super-hydrophilic micro-nano surface of the 3D printing nickel-titanium implant is urgently needed to overcome the defects of the prior art.
Disclosure of Invention
The invention aims to provide a preparation method of a super-hydrophilic micro-nano surface of a 3D printing nickel-titanium implant, which aims to solve the problems in the background technology.
In order to achieve the aim, the invention provides a preparation method of a super-hydrophilic micro-nano surface of a 3D printing nickel-titanium implant, which comprises the following steps:
s1, gradually polishing the surface of the 3D printed nickel-titanium implant by silicon carbide abrasive paper;
s2, carrying out vertical sand blasting treatment on the surface of the 3D printed nickel-titanium implant by using white corundum to obtain large fluctuation of tens of microns to tens of microns;
s3, carrying out 3D printing on the nickel-titanium implant after sand blasting, carrying out ultrasonic cleaning for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, carrying out blow-drying by using cold air, then, treating by using a mixed solution of hydrofluoric acid and nitric acid, washing the treated nickel-titanium implant by using a large amount of distilled water, and carrying out blow-drying by using the cold air, wherein the operation enables the surface of the nickel-titanium implant to form micron-sized fluctuation;
s4, placing the 3D printing nickel-titanium implant into a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then carrying out oxidation surface treatment for 5-10min by adopting voltage electrolysis, washing the treated nickel-titanium implant by deionized water, then drying, and forming a layer of oxidation film on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents a rough and porous appearance, the pore sizes are different, and the degree of identity with the surface of a human bone is high;
s5, performing alkaline etching treatment on the surface of the 3D printed nickel-titanium implant subjected to voltage electrolytic oxidation treatment by using a sodium hydroxide solution, and performing ultrasonic cleaning by using distilled water after the treatment is finished, so that a nano-sheet layer is covered on the micron-scale structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
As a further improvement of the technical scheme, in S2, white corundum with 80-180 meshes is used, the sand blasting pressure is 1.5-5bar, the sand blasting time is 60-120S, and the sand blasting distance is 5-15 cm.
As a further improvement of the technical scheme, in S3, the treatment time of the mixed solution of hydrofluoric acid and nitric acid is 90-180S, the solution temperature is room temperature, and the mass concentration of the hydrofluoric acid and the mass concentration of the nitric acid in the mixed solution are respectively 8-12% and 10-15%.
As a further improvement of the technical scheme, in the S4, the electrolysis voltage is 400-430V, the duty ratio is 30%, and the frequency is 90-100 Hz.
As a further improvement of the technical scheme, in the S5, the concentration of the sodium hydroxide solution is 5-10M, the solution temperature is 100-150 ℃, and the treatment time is 6-15 h.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the super-hydrophilic micro-nano surface of the 3D printing nickel-titanium implant, a micron-sized structure is constructed through mixed acid etching, then the nickel-titanium implant with the micron-sized structure is subjected to electrolytic oxidation surface treatment, so that the surface of the implant is formed into a coarse, porous and micron-sized structure with different apertures, the recognition degree with human bones is improved, and finally the implant is endowed with a micro-nano composite structure through alkali etching treatment, so that the surface of the implant has super-hydrophilicity.
Drawings
FIG. 1 is an overall flow diagram of the present invention;
FIG. 2 is an electron microscope image of the 3D nickel-titanium implant after the electrolytic oxidation treatment.
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.
Referring to fig. 1, a method for preparing a super-hydrophilic micro-nano surface of a 3D printed nickel-titanium implant according to the present invention is specifically described by the following specific examples.
The first embodiment is as follows:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant at a distance of 8cm under the pressure of 1.5bar for 120s, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 8%, and the mass concentration of the nitric acid is 10%. Ultrasonic treatment is carried out for 150s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 10min by adopting 400V voltage, the duty ratio is 30%, the frequency is 90Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) placing the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the molar concentration of 10M, treating for 12 hours at 100 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a nano-sheet layer is covered on the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example two:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant at a distance of 8cm under the pressure of 1.5bar for 120s, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 8%, and the mass concentration of the nitric acid is 12%. Ultrasonic treatment is carried out for 90s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 10min by adopting 400V voltage, the duty ratio is 30%, the frequency is 90Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) putting the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the molar concentration of 8M, treating for 10 hours at 100 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a nano-sheet layer is covered on the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example three:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant at a distance of 8cm under the pressure of 1.5bar for 120s, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 9%, and the mass concentration of the nitric acid is 15%. Ultrasonic treatment is carried out for 90s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 8min by adopting 410V voltage, the duty ratio is 30%, the frequency is 93Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) putting the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 8M, treating for 10 hours at 120 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer covers the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example four:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 15cm under the pressure of 3bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 11%, and the mass concentration of the nitric acid is 15%. Ultrasonic treatment is carried out for 90s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 8min by adopting 410V voltage, the duty ratio is 30%, the frequency is 93Hz, the nickel-titanium implant after treatment is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant after oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore sizes are different, and the identity degree with the surface of a human bone is high.
5. And (3) putting the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 10M, treating for 10 hours at 100 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer covers the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example five:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 15cm under the pressure of 3bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 11%, and the mass concentration of the nitric acid is 12%. Ultrasonic treatment is carried out for 120s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 7min by adopting 420V voltage, the duty ratio is 30%, the frequency is 96Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) putting the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 10M, treating for 6 hours at 150 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer is covered on the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example six:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 15cm under the pressure of 3bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 12%, and the mass concentration of the nitric acid is 14%. Ultrasonic treatment is carried out for 120s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 7min by adopting 420V voltage, the duty ratio is 30%, the frequency is 96Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) placing the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 5M, treating for 12 hours at 120 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer is covered on the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example seven:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 5cm under the pressure of 5bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 10%, and the mass concentration of the nitric acid is 13%. Ultrasonic treatment is carried out for 180s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 5min by adopting 430V voltage, the duty ratio is 30%, the frequency is 100Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) placing the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 5M, treating for 15 hours at 120 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer is covered on the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example eight:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Sand blasting: uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 5cm under the pressure of 5bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 10%, and the mass concentration of the nitric acid is 15%. Ultrasonic treatment is carried out for 90s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 5min by adopting 430V voltage, the duty ratio is 30%, the frequency is 100Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) placing the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 5M, treating for 12 hours at 150 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer covers the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Example nine:
1. and polishing the surface of the 3D printed nickel-titanium implant step by using silicon carbide abrasive paper.
2. Uniformly spraying 80-180-mesh white corundum on the 3D printed nickel-titanium implant for 60s at a distance of 5cm under the pressure of 5bar, ultrasonically cleaning the sprayed implant for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, and drying the implant by cold air.
3. The implant after sand blasting is placed into a mixed acid solution consisting of hydrofluoric acid and nitric acid, wherein the mass concentration of the hydrofluoric acid is 9%, and the mass concentration of the nitric acid is 15%. Ultrasonic treatment is carried out for 150s at room temperature, then a large amount of distilled water is used for cleaning, and cold air is used for drying, so that micron-scale fluctuation is formed on the surface of the nickel-titanium implant.
4. The 3D printing nickel-titanium implant is placed in a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then electrolytic oxidation surface treatment is carried out for 5min by adopting 430V voltage, the duty ratio is 30%, the frequency is 100Hz, the treated nickel-titanium implant is washed by deionized water and then dried, and a layer of oxide film is formed on the surface of the nickel-titanium implant subjected to oxidation surface treatment, so that the surface of the nickel-titanium implant presents rough and porous appearance, the pore diameters are different, and the recognition degree with the surface of human skeleton is high.
5. And (3) putting the implant subjected to voltage electrolytic oxidation treatment into a sodium hydroxide solution with the concentration of 10M, treating for 10 hours at 120 ℃, and ultrasonically cleaning by using distilled water after the treatment is finished, so that a layer of nanosheet layer covers the micron-sized structure on the surface of the nickel-titanium implant, and the surface of the implant with the ultra-high hydrophilic micro-nano composite structure is formed.
Test example 1
Scanning electron microscope observation is carried out on the surface of the treated 3D printed nickel-titanium implant in the first to ninth embodiments, and the result is shown in fig. 2, which shows that the nickel-titanium implant subjected to electrolytic oxidation treatment after the acid washing has uneven surface, many holes, rough surface and different pore sizes.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and the preferred embodiments of the present invention are described in the above embodiments and the description, and the present invention is not limited to the embodiments, and various changes and modifications may be made without departing from the spirit and scope of the present invention, and these changes and modifications fall within the scope of the claimed invention. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. A preparation method of a super-hydrophilic micro-nano surface of a 3D printing nickel-titanium implant is characterized by comprising the following steps:
s1, gradually polishing the surface of the 3D printed nickel-titanium implant by silicon carbide abrasive paper;
s2, carrying out vertical sand blasting treatment on the surface of the 3D printed nickel-titanium implant by using white corundum;
s3, carrying out 3D printing on the nickel-titanium implant subjected to sand blasting, carrying out ultrasonic cleaning for 15min by using distilled water, acetone, absolute ethyl alcohol and distilled water in sequence, carrying out blow-drying by using cold air, then, treating by using a mixed solution of hydrofluoric acid and nitric acid, washing the treated nickel-titanium implant by using a large amount of distilled water, and carrying out blow-drying by using cold air;
s4, placing the 3D printed nickel-titanium implant into a mixed solution of calcium acetate and beta-glycerophosphoric acid disodium salt, then carrying out oxidation surface treatment for 5-10min by adopting voltage electrolysis, washing the treated nickel-titanium implant by deionized water, and then drying;
and S5, performing alkaline etching treatment on the surface of the 3D printed nickel-titanium implant subjected to voltage electrolytic oxidation treatment by using a sodium hydroxide solution, and performing ultrasonic cleaning by using distilled water after the treatment is finished.
2. The preparation method of the 3D printing nickel-titanium implant super-hydrophilic micro-nano surface according to claim 1, characterized in that: in the S2, white corundum with 80-180 meshes is used, the sand blasting pressure is 1.5-5bar, the sand blasting time is 60-120S, and the sand blasting interval is 5-15 cm.
3. The preparation method of the 3D printing nickel-titanium implant super-hydrophilic micro-nano surface according to claim 1, characterized in that: in the S3, the treatment time of the mixed solution of hydrofluoric acid and nitric acid is 90-180S, the solution temperature is room temperature, the mass concentration of the hydrofluoric acid in the mixed solution is 8-12%, and the mass concentration of the nitric acid in the mixed solution is 10-15%.
4. The preparation method of the 3D printing nickel-titanium implant super-hydrophilic micro-nano surface according to claim 1, characterized in that: in S4, the electrolysis voltage is 400-430V, the duty ratio is 30%, and the frequency is 90-100 Hz.
5. The preparation method of the 3D printing nickel-titanium implant super-hydrophilic micro-nano surface according to claim 1, characterized in that: in the S5, the concentration of the sodium hydroxide solution is 5-10M, the solution temperature is 100-150 ℃, and the treatment time is 6-15 h.
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