CN117530764A - Magnesium alloy hollow nail, magnesium alloy guide pin, preparation method and application thereof - Google Patents
Magnesium alloy hollow nail, magnesium alloy guide pin, preparation method and application thereof Download PDFInfo
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- CN117530764A CN117530764A CN202311490029.8A CN202311490029A CN117530764A CN 117530764 A CN117530764 A CN 117530764A CN 202311490029 A CN202311490029 A CN 202311490029A CN 117530764 A CN117530764 A CN 117530764A
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- magnesium alloy
- hollow nail
- alloy hollow
- guide pin
- nail body
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 332
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000005260 corrosion Methods 0.000 claims abstract description 51
- 238000005524 ceramic coating Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 32
- 239000011248 coating agent Substances 0.000 claims description 30
- 239000011777 magnesium Substances 0.000 claims description 24
- 239000011575 calcium Substances 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 23
- 239000011701 zinc Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 20
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 16
- 239000012535 impurity Substances 0.000 claims description 15
- 229910052791 calcium Inorganic materials 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims description 10
- 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 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- PJAIMBYNTXNOCN-UHFFFAOYSA-N 3,6-dibromo-1h-indole Chemical compound BrC1=CC=C2C(Br)=CNC2=C1 PJAIMBYNTXNOCN-UHFFFAOYSA-N 0.000 claims description 9
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 9
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 9
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000007797 corrosion Effects 0.000 abstract description 44
- 230000015556 catabolic process Effects 0.000 abstract description 25
- 238000006731 degradation reaction Methods 0.000 abstract description 25
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 238000002474 experimental method Methods 0.000 description 25
- 239000000956 alloy Substances 0.000 description 23
- 210000000988 bone and bone Anatomy 0.000 description 21
- 238000002513 implantation Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- 229910045601 alloy Inorganic materials 0.000 description 17
- 238000004458 analytical method Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000007943 implant Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000338 in vitro Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 208000010392 Bone Fractures Diseases 0.000 description 5
- 206010017076 Fracture Diseases 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 229910004860 CaZn Inorganic materials 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000001727 in vivo Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 230000000399 orthopedic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 230000006399 behavior Effects 0.000 description 2
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- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 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
- 238000000465 moulding Methods 0.000 description 2
- 238000012803 optimization experiment Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000004080 punching Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 230000008093 supporting effect Effects 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009672 coating analysis Methods 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006237 degradable polymer Polymers 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 210000003041 ligament Anatomy 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
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- 238000005457 optimization Methods 0.000 description 1
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- 238000001953 recrystallisation Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical class [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
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- 238000001356 surgical procedure Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
- A61B17/864—Pins or screws or threaded wires; nuts therefor hollow, e.g. with socket or cannulated
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/68—Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
- A61B17/84—Fasteners therefor or fasteners being internal fixation devices
- A61B17/86—Pins or screws or threaded wires; nuts therefor
- A61B17/866—Material or manufacture
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/88—Osteosynthesis instruments; Methods or means for implanting or extracting internal or external fixation devices
- A61B17/8897—Guide wires or guide pins
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B17/56—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
- A61B17/58—Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
- A61B17/88—Osteosynthesis instruments; Methods or means for implanting or extracting internal or external fixation devices
- A61B17/90—Guides therefor
-
- 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
-
- 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
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/16—Electrodes characterised by the combination of the structure and the material
-
- 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
-
- 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
- C25D11/30—Anodisation of magnesium or alloys based thereon
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00526—Methods of manufacturing
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61B—DIAGNOSIS; SURGERY; IDENTIFICATION
- A61B17/00—Surgical instruments, devices or methods, e.g. tourniquets
- A61B2017/00831—Material properties
- A61B2017/0088—Material properties ceramic
Abstract
The invention discloses a magnesium alloy hollow nail, a magnesium alloy guide pin, a preparation method and application thereof, wherein the magnesium alloy hollow nail consists of a magnesium alloy hollow nail body and a layer of inorganic ceramic coating coated on the surface of the magnesium alloy hollow nail body; the magnesium alloy hollow nail body is provided with a through hole for a magnesium alloy guide pin to penetrate through along a central shaft, and the inorganic ceramic coating is also uniformly distributed on all inner surfaces of the through hole; the outer wall of the magnesium alloy hollow nail body is provided with threaded parts along the length direction; the self-corrosion potential of the inorganic ceramic coating is higher than that of the magnesium alloy hollow nail body. The magnesium alloy guide pin is used for being matched with the magnesium alloy hollow nail, is of a rod-shaped structure, and has an outer diameter matched with the inner diameter of a through hole of the magnesium alloy hollow nail. The magnesium alloy hollow nail is matched with the magnesium alloy guide pin, so that the corrosion resistance of the magnesium alloy hollow nail is obviously improved, the service life of the magnesium alloy hollow nail is prolonged, and the magnesium alloy hollow nail has good biocompatibility and longer degradation period.
Description
Technical Field
The invention relates to the technical field of medical instruments, in particular to a magnesium alloy hollow nail, a preparation method and application thereof.
Background
At present, various alloy bone nails are widely applied to bone clinical operations, the bone nails are generally used for fixing internal fracture or dislocation, and the internal implants such as two different bone blocks or fixed bone plates are directly screwed to fix the fracture, position bones and promote the recovery of the bones. According to different structural characteristics, bone nails can be classified into common screws, locking screws, headless screws (also called Hab nails), hollow nails, and the like. Bone nails can be classified into titanium nails, stainless steel nails, and bioabsorbable screws according to the manufacturing materials. Under the background of aging population in China, the number of fracture patients is increased, the demand of the market for bone nails is increased, and higher requirements are put on the performance of the alloy orthopedic implant device, such as better corrosion resistance, longer service period, in-vivo degradable performance and the like.
Compared with the traditional orthopedic implantation instruments such as stainless steel, cobalt-based alloy, titanium alloy and the like, the magnesium alloy implantation instrument has the following advantages: on one hand, the magnesium alloy bone nail can be degraded and absorbed after the damaged bone tissue is repaired, and the magnesium alloy bone nail does not need to be taken out by a secondary operation, so that the pain and the treatment cost of a patient can be reduced; on the other hand, the density and the elastic modulus of the magnesium alloy are closer to those of human bone tissue, so that the stress shielding effect can be reduced, and the healing of the bone tissue is facilitated. Therefore, in recent years, magnesium alloy orthopedic implant devices are rapidly developing.
However, the magnesium alloy implantation apparatus has the problem of short service life, which is determined by the characteristics of the material. Because magnesium and magnesium alloy degrade fast in body fluid, produce hydrogen more easy to produce the gasbag in the short term, after being implanted in vivo, the mechanical service life is short. The main means for improving the service period of the magnesium alloy implantation instrument at present is based on the improvement of a single bone screw material body, so that the corrosion resistance of the magnesium alloy implantation instrument is improved, but the synergistic effect among a plurality of parts in the whole implantation instrument system is not considered, the risk of mechanical property failure after the implantation of the magnesium alloy bone screw still exists, and the service period is difficult to effectively prolong.
In addition, the existing magnesium alloy surface treatment method can delay the degradation rate at the initial stage of implantation and reduce the generation of hydrogen gas bags, but the degradation mode is mainly point corrosion, so that the mechanical support time of nails in the body is short, and the problem of high repair probability exists. For example, patent publication CN 108543118B discloses an in-vivo controllable degradable magnesium alloy fixing screw, the prepared magnesium alloy screw body is of a conventional solid screw structure, the clinical application range is limited, an oxide film layer with the thickness of 50-200 μm is formed on the magnesium alloy screw body, a degradable polymer coating with the thickness of 1-50 μm is coated on the oxide film layer, the thickness of the two coatings is larger, the two coatings are easy to fall off in the use process to cause local corrosion, and the effect of remarkably improving the service period cannot be achieved. The patent of the issued publication number CN109295365B discloses a degradable magnesium alloy molding blank, and the patent scheme only solves the problem of poor molding mechanical property of a magnesium alloy material, but cannot solve the problems of high degradation rate, non-uniformity and uncontrollable magnesium alloy, and the service period is difficult to be obviously prolonged.
Therefore, the existing magnesium alloy bone screw implantation instrument is based on the problems that the degradation speed of the bone screw is too high, the bone screw is uneven and the service period is short due to the improvement of the material performance of the bone screw, and the technical effect is difficult to be remarkably improved.
Accordingly, there is a need for further improvements in the art.
Disclosure of Invention
Aiming at the problems, the invention provides a novel magnesium alloy hollow nail, which is matched with a magnesium alloy guide pin penetrating through the magnesium alloy hollow nail, so that the magnesium alloy hollow nail with high open circuit potential is protected in a manner of sacrificing the magnesium alloy guide pin, and the magnesium alloy hollow nail can provide longer mechanical support as a main body bearing unit of an implantation instrument, and the service period of the magnesium alloy hollow nail is effectively prolonged.
In order to solve the problems, the application provides the following technical scheme:
in a first aspect, the present application provides a magnesium alloy hollow nail, which is composed of a magnesium alloy hollow nail body and a layer of inorganic ceramic coating coated on the surface of the magnesium alloy hollow nail body; the magnesium alloy hollow nail body is provided with a through hole for a magnesium alloy guide pin to penetrate through along a central shaft, and the inorganic ceramic coating is also uniformly distributed on all inner surfaces of the through hole; the outer wall of the magnesium alloy hollow nail body is provided with threaded parts along the length direction; the self-corrosion potential of the inorganic ceramic coating is higher than that of the magnesium alloy hollow nail body.
Although the existing hollow nails also have an inner hole, the inner hole or cavity is used for injecting and releasing the medicine, such as the patent publication No. CN 111282025B.
In the scheme of this application, run through the through-hole that sets up in the hollow nail of magnesium alloy is for being used for installing the magnesium alloy guide pin, and this application is through increase at the surface of the hollow nail of magnesium alloy behind the inorganic ceramic coating, makes the self corrosion potential of the hollow nail of magnesium alloy be higher than the self corrosion potential of the magnesium alloy guide pin of the same material to make the magnesium alloy guide pin play the role of sacrificial anode, form relative electrochemical corrosion protection, make the hollow nail of magnesium alloy that open circuit potential is high protected, can provide longer mechanical support as main part bearing unit, greatly prolonged whole implantation apparatus's service life. It can be seen that the corrosion resistance principle of the magnesium alloy hollow nail is different from the prior art.
In order to facilitate the normal implantation of the magnesium alloy hollow nail to a target position, the outer wall of the magnesium alloy hollow nail body is provided with threaded parts along the length direction. The structure and distribution of the screw parts are not limited to the specific embodiments and the drawings.
Optionally, in the magnesium alloy hollow nail, the thread part comprises a first thread part I and a second thread part II which are distributed on the outer side surface of the magnesium alloy body, and the two thread parts are adjacently arranged or are arranged at a certain distance. The threads of the two threaded portions may be provided differently.
Optionally, in the magnesium alloy hollow nail, in order to be convenient for install the hollow nail, the outer terminal surface of head is provided with tightly decides the groove, tightly decides the groove and communicates with the through-hole, tightly decides the cross section of groove and is non-circular.
Optionally, in the magnesium alloy hollow nail, the magnesium alloy hollow nail body material comprises the following components in percentage by mass: 1.0-6.0% of Ca, 0.8-1.2% of Zn, less than 0.1% of impurity total amount and the balance of Mg. The magnesium alloy hollow nail body prepared by the method has good corrosion resistance.
Preferably, the magnesium alloy hollow nail body material comprises the following components in percentage by mass: 2%/4% Ca, 1% Zn, less than 0.1% total impurities, and the balance Mg.
Preferably, the preparation method of the magnesium alloy hollow nail body comprises the following steps:
(1) Under the protection of the atmosphere of the mixed protective gas, melting pure magnesium at 750-800 ℃, and preserving heat for 30-60 min; adding high-purity zinc and pure calcium with corresponding mass percentages, mechanically stirring for 3-5min, and preserving heat for 20-30 min; cooling to 700-730 ℃ and casting into cast ingots;
(2) Performing a low-temperature extrusion molding process under the conditions that the extrusion ratio is 20-80, the extrusion temperature is 250-400 ℃ and the extrusion shaft speed is 0.1-1.0 mm/s, so as to obtain a magnesium alloy bar; and then the magnesium alloy bar is subjected to physical processing by a lathe to obtain the magnesium alloy hollow nail body with the structural characteristics.
Optionally, in the magnesium alloy hollow nail, the inorganic ceramic coating is an arc oxidation coating, which comprises the following elements in percentage by mass: 20-40% of Mg, 20-40% of O, 8-20% of P, 3-6% of Ca and 15-25% of F.
In a second aspect, the present application further provides a magnesium alloy guide pin for use in cooperation with the aforementioned magnesium alloy hollow nail, where the magnesium alloy guide pin has a rod-shaped structure, and an outer diameter of the magnesium alloy guide pin is slightly smaller than an inner diameter of a through hole of the magnesium alloy hollow nail. The length of the magnesium alloy guide pin is longer than that of the magnesium alloy hollow nail, so that the two ends of the magnesium alloy guide pin are exposed outside in an assembled state, and the magnesium alloy guide pin is convenient to play a role.
The material of the magnesium alloy guide pin is the same as that of the magnesium alloy hollow nail body. Thus greatly simplifying the material types of the magnesium alloy implantation instrument (the assembly of the magnesium alloy hollow nail and the guide pin) and reducing the processing technology and the production cost thereof.
Preferably, the material of the magnesium alloy guide pin comprises the following components in percentage by mass: 1.0-6.0% of Ca, 0.8-1.2% of Zn, less than 0.1% of impurity total amount and the balance of Mg.
In a third aspect, the present application further provides a method for preparing the magnesium alloy guide pin, which includes the following steps: firstly, preparing a magnesium alloy bar, and processing the magnesium alloy bar into a magnesium alloy guide pin through a lathe; wherein the magnesium alloy bar comprises the following components in percentage by mass: 1.0-6.0% of Ca, 0.8-1.2% of Zn, less than 0.1% of impurity total amount and the balance of Mg.
In a fourth aspect, the present application further provides a method for preparing the magnesium alloy hollow nail, which includes the following steps:
s1, preparing a magnesium alloy bar, and processing the magnesium alloy bar into a magnesium alloy hollow nail body through a lathe;
wherein the magnesium alloy bar comprises the following components in percentage by mass: 1.0 to 6.0 percent of Ca, 0.8 to 1.2 percent of Zn, less than 0.1 percent of impurity total amount and the balance of Mg;
s2, processing an inorganic ceramic coating on the surface of the magnesium alloy hollow nail body to obtain the magnesium alloy hollow nail.
Preferably, in the preparation method of the magnesium alloy hollow nail, the preparation method of the magnesium alloy bar comprises the following steps:
s11, melting pure magnesium at 750-800 ℃ under the protection of the atmosphere of the mixed protective gas, and preserving heat for 30-60 min; adding high-purity zinc and pure calcium with corresponding mass percentages, mechanically stirring for 3-5min, and preserving heat for 20-30 min; cooling to 700-730 ℃ and casting into cast ingots;
s12, performing a low-temperature extrusion molding process under the conditions that the extrusion ratio is 20-80, the extrusion temperature is 250-400 ℃ and the extrusion shaft speed is 0.1-1.0 mm/S, thereby obtaining the magnesium alloy bar.
Preferably, the method for processing the inorganic ceramic coating comprises the following steps:
s21, respectively weighing corresponding amounts of nano hydroxyapatite, glycol and triethanolamine, adding the nano hydroxyapatite, the glycol and the triethanolamine into water to prepare a solution A, and placing the solution A into an ultrasonic generator for ultrasonic assisted curing for 40-60min;
s22, weighing sodium hexametaphosphate and potassium fluoride dihydrate, and adding the sodium hexametaphosphate and the potassium fluoride dihydrate into water to prepare a solution B;
s23, slowly adding the solution A with the same volume into the solution B, and uniformly stirring to obtain a solution C;
s24, placing the cleaned magnesium alloy hollow nail body in a solution C to serve as an anode, and taking stainless steel as a cathode to perform micro-arc oxidation treatment;
and S25, washing the magnesium alloy hollow nails obtained in the previous step with water and ethanol in sequence, and drying.
Optionally, in step S21, in the solution A, the mass concentration of nano hydroxyapatite is 3-5g/L, the volume concentration of ethylene glycol is 15-25ml/L, and the volume concentration of triethanolamine is 25-35ml/L.
Optionally, in step S22, in the solution B, the mass volume concentration of sodium hexametaphosphate is 4-8g/L, and the mass volume concentration of potassium fluoride dihydrate is 14-18g/L.
Preferably, the conditions of the micro-arc oxidation treatment are as follows: the positive voltage is 340-420V, the positive duty ratio is 5-15%, the power frequency is 800-1200Hz, the negative voltage is 50-80V, the negative duty ratio is 5-10%, the positive and negative pulse ratio is 5-10:1, the treatment time is 10-20min.
Further preferably, the conditions of the micro-arc oxidation treatment are as follows: the micro-arc oxidation process parameters are set to 400V, the frequency is 1000Hz, the duty ratio is 10%, and the treatment time is 10min.
In a fifth aspect, the present application provides an application method of the magnesium alloy hollow nail, where the application method is as follows: and assembling the magnesium alloy hollow nail and a magnesium alloy guide pin penetrating through the through hole of the magnesium alloy hollow nail. Wherein, the two ends of the magnesium alloy guide pin are exposed outside the magnesium alloy guide pin, and the material of the magnesium alloy guide pin is the same as the material of the magnesium alloy hollow nail body.
Optionally, the concrete using method of the magnesium alloy hollow nail and the matched magnesium alloy guide pin comprises the following steps:
in the operation process, firstly, after punching a fracture site (or an operation site), firstly screwing a stainless steel guide pin into the punching site to firstly position, then installing the magnesium alloy hollow pin in place along the stainless steel guide pin, and then screwing out the stainless steel guide pin and replacing the stainless steel guide pin with the magnesium alloy guide pin, namely, installing the magnesium alloy guide pin into the penetrating magnesium alloy hollow pin, thereby completing the fixation of the magnesium alloy implantation instrument to the fracture site. The stainless steel guide needle with higher mechanical strength is adopted for positioning first, so that the damage of the magnesium alloy guide needle can be avoided. In other application modes, the method can also directly adopt the method that the magnesium alloy guide pin is implanted first and then the magnesium alloy hollow nail is implanted. The application of the cruciate ligament reconstruction surgery is similar and will not be described in detail.
The invention has the following beneficial effects:
1. the invention provides a magnesium alloy hollow nail made of a specific material, wherein a through hole is formed in the magnesium alloy hollow nail along the axis for installing a magnesium alloy guide pin, and an inorganic ceramic coating is wrapped on the surface of a magnesium alloy hollow nail body material, so that the self-corrosion potential of the inorganic ceramic coating is higher than that of the magnesium alloy hollow nail body, and the implanted magnesium alloy hollow nail and the guide pin have galvanic corrosion effect after being surgically implanted into a focus part.
The principle of corrosion prevention of the magnesium alloy hollow nail body is as follows: the magnesium alloy guide pin plays a role of a sacrificial anode due to low self-corrosion potential, so that relative electrochemical corrosion protection is formed, and the magnesium alloy guide pin starts to directionally corrode from two ends, so that the problems of high degradation rate, uneven degradation and short service period of the existing magnesium alloy can be solved; by the method, the magnesium alloy hollow nail with high open circuit potential is protected, and can provide longer mechanical support as a main body bearing unit, thereby greatly prolonging the service life of the whole implantation instrument.
2. The inorganic ceramic coating coated on the inner surface and the outer surface of the magnesium alloy hollow nail plays two roles: the first effect is that the arrangement of the coating enables the magnesium alloy guide pin to function as a sacrificial anode, thereby protecting the hollow pin body. The second effect is: the coating has better corrosion resistance in an in-vivo environment, and can independently establish a corrosion barrier for the magnesium alloy hollow nail after the sacrificial anode is degraded and corroded in the later stage of instrument implantation, so that the degradation and the mechanical integrity attenuation of the magnesium alloy hollow nail are delayed. Therefore, the magnesium alloy hollow nail has double protection effects through the double technical means of the sacrificial anode and the coating, and the sacrificial anode and the coating are compatible and mutually promoted, so that the magnesium alloy hollow nail has excellent mechanical supporting force, remarkably prolonged service life of the instrument, good biocompatibility and longer degradation period.
3. The raw materials of the magnesium alloy hollow nail only comprise Mg, ca and Zn, the total content of impurities is lower than 0.1 percent, the magnesium alloy hollow nail also has good biosafety, and the inorganic ceramic coating has good biocompatibility, so that the magnesium alloy implantation instrument is safe to use.
4. The magnesium alloy hollow nail is characterized in that a body is obtained by physical processing of a magnesium alloy bar, then the processing of a coating is completed by one-step micro-arc oxidation treatment, the raw material composition is simple, the whole preparation process is simple and easy to operate, toxic and harmful substances are not involved, and the magnesium alloy hollow nail is environment-friendly and environment-friendly.
Drawings
FIG. 1 is a diagram of a magnesium alloy bar;
FIG. 2 is a pictorial view of one embodiment of a magnesium alloy hollow staple; the method comprises the steps of carrying out a first treatment on the surface of the
FIG. 3 is a schematic structural view of a magnesium alloy implantation instrument;
FIG. 4 is a view of the surface of the alloy after corrosion;
FIG. 5 is a graph showing experimental results of the effect of voltage on the coating;
FIG. 6 is a graph showing the results of the evaluation experiments of the degradation rates of the surface coatings of different materials;
FIG. 7 is a microstructure of a magnesium alloy hollow extruded bar of example 4;
FIG. 8 is a surface EDS qualitative result of Mg2Ca1 Zn;
FIG. 9 shows the second phase area fraction results in Mg2Ca1Zn alloy;
FIG. 10 is a graph showing the open circuit potential and corrosion current density measurement results of the alloy of example 4;
FIG. 11 is a schematic diagram of a hydrogen separation apparatus;
FIG. 12 is a magnesium alloy bodyDegradation of H 2 A release profile;
FIG. 13 is an SEM image of a through hole of a magnesium alloy hollow nail with or without a coating;
FIG. 14 is an SEM image of the outer surface of the ceramic coating of the magnesium alloy hollow staple.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention. In the present invention, the equipment, materials, etc. used are commercially available or commonly used in the art, unless otherwise specified. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1 preparation of magnesium alloy hollow spike and magnesium alloy guide needle
The magnesium alloy hollow nail mainly has the following three improvements: firstly, the structure is improved, secondly, the material of the magnesium alloy hollow nail body is improved, thirdly, the inorganic ceramic coating attached to the outside of the magnesium alloy hollow nail body is improved, and the following parts are respectively explained:
1. structure arrangement of magnesium alloy hollow nail
The embodiment provides a new magnesium alloy hollow nail, and fig. 2 and 3A show an embodiment of the magnesium alloy hollow nail, and for matching with the structure of a magnesium alloy guide pin (the material of the guide pin is the same as that of a magnesium alloy hollow nail body) used in combination, the structure of the hollow nail is as follows:
the magnesium alloy hollow nail consists of a magnesium alloy hollow nail body 11 and a layer of inorganic ceramic coating 12 coated on the surface of the magnesium alloy hollow nail body. The magnesium alloy hollow nail body is provided with a through hole 13 for the magnesium alloy guide pin to penetrate through along the central shaft, and the inorganic ceramic coating is uniformly distributed on the outer surface of the hollow nail body and all inner surfaces of the through hole.
The outer wall of the magnesium alloy hollow nail body is provided with threaded parts along the length direction. In this embodiment, preferably, the threaded portion includes a first threaded portion I and a second threaded portion II distributed on the outer side surface of the magnesium alloy body, and the two threaded portions are disposed adjacently. The structure and distribution of the screw parts are not limited to the specific embodiments and the drawings.
In order to facilitate the installation of the hollow nail, the outer end face of the head part is provided with a fastening groove which is communicated with the through hole, and the cross section of the fastening groove is non-circular, such as plum blossom shape, inner hexagon shape and the like. In the use process, the hollow nail can be screwed into the target position by operating the tool through the matching of the tail end of the tool (such as a screwdriver or a spanner) and the fastening groove. The fastening groove can be a groove hole with various shapes in the prior art, and is not limited to the quincuncial groove hole in the embodiment.
More importantly, the self-corrosion potential of the inorganic ceramic coating is higher than that of the magnesium alloy hollow nail body, so that the magnesium alloy hollow nail with high open circuit potential is protected in a mode of sacrificing the magnesium alloy guide pin, and the magnesium alloy hollow nail serving as a main bearing unit can provide longer mechanical support.
The magnesium alloy hollow nail body material comprises the following components in percentage by mass: 1.0 to 6.0 percent of Ca, 0.8 to 1.2 percent of Zn, less than 0.1 percent of impurity total amount and the balance of Mg; the magnesium alloy guide pin and the magnesium alloy hollow nail body are made of the same material.
The inorganic ceramic coating is a micro-arc oxidation coating and comprises the following components in percentage by mass: 20-40% of Mg, 20-40% of O, 8-20% of P, 3-6% of Ca and 15-25% of F.
2. Preparation method of magnesium alloy hollow nail
The embodiment provides a preparation method of the magnesium alloy hollow nail, which comprises the following steps:
s1, preparing a magnesium alloy bar, and processing the magnesium alloy bar into a magnesium alloy hollow nail body through a lathe;
s11, mixing protective gas (99% CO) 2 +1% SF6), melting pure magnesium at 760 ℃, and preserving heat for 30-60 min; adding high-purity zinc and pure calcium, mechanically stirring for 3-5min, and preserving heat for 20-30 min; cooling to 72Casting into cast ingot at 0 ℃.
S12, processing the cast ingot by a low-temperature extrusion molding process under the conditions that the extrusion ratio is 20-80, the extrusion temperature is 250-400 ℃ and the extrusion shaft speed is 0.1-1.0 mm/S to obtain a magnesium alloy bar (shown in figure 1).
S13, machining by a longitudinal cutting numerical control lathe to obtain the magnesium alloy hollow nail body (shown in the upper diagram of fig. 2).
S2, processing an inorganic ceramic coating on the surface of the magnesium alloy hollow nail body to obtain the magnesium alloy hollow nail.
Specifically, the processing method of the inorganic ceramic coating comprises the following steps:
s21, weighing nano hydroxyapatite, glycol and triethanolamine according to a proportion, adding the nano hydroxyapatite, the glycol and the triethanolamine into water to prepare 1L of solution A, and placing the solution A into an ultrasonic generator to perform ultrasonic assisted curing for 40-60min.
Wherein the particle size of the nano hydroxyapatite is less than 100 nanometers. In 1L of solution A, the dosage of nano hydroxyapatite is 3-5g, the dosage of glycol is 15-25ml, and the dosage of triethanolamine is 25-35ml.
S22, weighing sodium hexametaphosphate and potassium fluoride dihydrate, and adding the sodium hexametaphosphate and the potassium fluoride dihydrate into water to prepare 1L of solution B.
Wherein, the mass of the sodium hexametaphosphate is 4-8g, and the mass of the potassium fluoride dihydrate is 14-18g.
S23, slowly adding the solution A into the solution B, and uniformly stirring to obtain the solution C.
S24, placing the cleaned magnesium alloy hollow nail body in a solution C to serve as an anode, and taking stainless steel as a cathode to perform micro-arc oxidation treatment.
The conditions of the micro-arc oxidation treatment are as follows: the positive voltage is 340-420V, the positive duty ratio is 5-15%, the power frequency is 800-1200Hz, the negative voltage is 0-30V, the negative duty ratio is 20-80%, the positive and negative pulse ratio is 5-10:1, the treatment time is 10-20min.
And S25, washing the magnesium alloy hollow nail obtained in the previous step with water and ethanol in sequence, and drying to obtain the magnesium alloy hollow nail with the surface biological ceramic coating (as shown in the lower part of the figure 2).
The magnesium alloy hollow nails of the following three experimental groups were respectively set according to the above preparation method and the specific conditions of the following table 1, and the specific formulas and processing conditions are shown in the following table 1.
Table 1 three sets of magnesium alloy hollow nails were prepared under the following conditions
3. Preparation of magnesium alloy guide pin
Because the material of the magnesium alloy guide pin is the same as that of the magnesium alloy hollow nail body, the preparation method is the same as that of the magnesium alloy hollow nail body, and the difference is that: when the magnesium alloy bar is processed by adopting a longitudinal cutting numerical control lathe, the magnesium alloy bar is processed into the magnesium alloy guide pin 2.
Based on the reasons, the material performance characteristics of the magnesium alloy guide pin are the same as those of the magnesium alloy hollow nail body, and the magnesium alloy guide pin can be analyzed by referring to the experimental data of the subsequent magnesium alloy hollow nail. And will not be described in detail later.
4. Performance test of magnesium alloy hollow nails of experimental groups 1-3
(1) Detection method
The open circuit potential and the corrosion current density of the magnesium alloy hollow nails in the experimental groups 1-3 are measured, and the detection method refers to the 1 st part of the GB/T228.1 metal material tensile test, namely the open circuit potential measurement method for evaluating the long-term corrosion behaviors of metal implant materials and medical instruments by using a room temperature test method YY/T1552-2017 surgical implant.
(2) Detection results and analysis
The test results are shown in the following table 2, and it is clear from the results of the table that the open circuit potential values of the magnesium alloy hollow nails of the test groups 1 to 3 are close to zero, which indicates that the corrosion resistance is good. The open-circuit potential of the hollow nail with the coating is increased, and a potential difference exists between the magnesium alloy material (equivalent to a magnesium alloy guide pin) without the coating, so that the magnesium alloy hollow nail and the magnesium alloy guide pin can be matched with each other to play a role.
TABLE 2 alloy open circuit potential and current density for three groups of magnesium alloy hollow nails (coated)
| Sample numbering | Experiment group one | Experiment group II | Experiment group III |
| Open circuit potential (V) | -0.185 | -0.093 | -0.086 |
| Current Density (×10) -6 A/cm 2 ) | 3.351 | 3.126 | 3.279 |
Example 2 comparison of Properties of magnesium alloy hollow nails before and after inorganic ceramic coating processing
In the embodiment, two groups of magnesium alloy hollow nails are used as experimental objects, one group is 2CaZn, and the body materials of the magnesium alloy hollow nails comprise the following components: 2% of Ca, 1% of Zn, less than 0.1% of impurity total amount and the balance of Mg; the other group is 4CaZn, and the body material composition of the magnesium alloy hollow nail of the group is as follows: 4% of Ca, 1% of Zn, less than 0.1% of impurity and the balance of Mg. Other processing conditions were the same as in experimental group 1 of example 1.
The open circuit potential and the corrosion current density changes of the two groups of magnesium alloy hollow nails before and after the inorganic ceramic coating (i.e. MAO treatment) is added are detected, so that the corrosion resistance is analyzed.
1. The detection method comprises the following steps:
and using an electrochemical workstation, wherein the electrolyte is 0.9% sodium chloride solution, the reference electrode is a saturated silver chloride electrode, switching to an open circuit potential gear, setting an operation parameter for measurement, switching to a polarization curve gear, and measuring after setting the operation parameter.
2. Experimental results and analysis
As can be seen from the results of tables 3 to 4 and FIG. 10, the open circuit potential of the magnesium alloy hollow nail body of the present application was significantly reduced to-0.115V and the corrosion current density was reduced to 3.16X10 after the addition of the inorganic ceramic coating (i.e., MAO treatment) -6 A/cm 2 。
The detection result shows that: after the inorganic ceramic coating is added on the surface of the magnesium alloy hollow nail body (also the magnesium alloy bar), the corrosion tendency of the magnesium alloy hollow nail body is reduced to 1/6 of that of the original magnesium alloy hollow nail body, and the corrosion resistance is greatly improved.
TABLE 3 open circuit potential and current density of untreated magnesium alloy hollow staple bodies
TABLE 4 open circuit potential and current density of magnesium alloy hollow nail body after increasing inorganic ceramic coating
Example 3 comparison of Performance of different modes of use of the magnesium alloy implant device of the present invention
1. Experimental method
The following experimental group 1 and comparative examples 1 and 2 of example 1 were set, respectively, and in vitro simulated degradation experiments were performed using the instruments of experimental group 8 and comparative examples 1 and 2 as objects, and in vitro simulated magnesium alloy degradation experimental apparatus (i.e., schematic diagram of hydrogen evolution experimental apparatus) as shown in fig. 11, which measures the hydrogen generation volume by a drainage method, thereby obtaining degradation rate of magnesium alloy.
(1) The experimental groups were specifically set as follows:
experiment group 1: a magnesium alloy implantation instrument (assembly of magnesium alloy hollow and the like and magnesium alloy guide pin) prepared according to the method of experimental group 1 of example 1;
comparative example 1: the differences from experimental group 1 are: only providing a magnesium alloy hollow nail (with a coating), and no built-in magnesium alloy guide pin;
comparative example 2: the differences from experimental group 1 are: only the magnesium alloy hollow nail body is provided, and no inorganic ceramic coating and no built-in magnesium alloy guide pin are arranged on the magnesium alloy hollow nail body.
Comparative example 3: the existing magnesium alloy WE43 was used.
(2) Specific experimental steps and conditions: each group of magnesium alloy instruments was immersed in PBS buffer solution, and the specific apparatus was installed as shown in fig. 11, and after the installation, the volume of hydrogen gas drainage and the indoor temperature were recorded every day, and the degradation simulation liquid was replaced every week.
2. Experimental results and analysis
Samples from each test group were simulated in vitro degradation in PBS buffer for 2 months as described above, and the cumulative volume of hydrogen release for each group of magnesium alloy is shown in fig. 12. The hydrogen release rates of the 3 test groups of magnesium alloy implant devices were close during the first week of simulated degradation, and then differed:
(1) uncoated, guide pin-free comparative example 2: the surface of the hollow nail body forms obvious pitting points, the hydrogen release volume is rapidly increased, the nail loses mechanical support effect after degradation for 30 days, and the nail breaks at corrosion points.
(2) Comparative example 1 of coated magnesium alloy hollow nails: the magnesium alloy hollow nail has stable hydrogen release rate, the release curve is linear, the magnesium alloy hollow nail is degraded within 30 days and is biased to be uniformly corroded, after 30 days, a point of corrosion appears, and after 60 days of degradation, the nail loses mechanical support and breaks.
(3) Comparative example 3: magnesium alloy WE4 was crushed and degraded within a week.
(4) Experiment group 1: the magnesium alloy hollow nails of the group are provided with the coating and are matched with the magnesium alloy hollow nails, so that the hydrogen release rate is slow, uniform and stable, after 60 days of continuous degradation, the two ends of the nails are corroded, the middle section is not provided with a point of corrosion, the mechanical supporting effect can be maintained, and the complete degradation period of the magnesium alloy equipment of the group is estimated to be 2 years according to the earlier hydrogen release rate.
Based on the experimental results, the magnesium alloy implantation instrument provided by the application ensures that the magnesium alloy hollow nail with high open circuit potential is protected in a manner of sacrificing the magnesium alloy guide pin by the mutual matching of the magnesium alloy hollow nail with the self-corrosion potential difference and the magnesium alloy guide pin, and can provide longer mechanical support as a main body bearing unit.
Example 4 optimization experiments on magnesium alloy hollow spike body Material
1. The experimental method comprises the following steps:
(1) Preparation of magnesium alloy hollow nail body material (or magnesium alloy guide pin):
in this example, experimental groups 4 to 7 were set, and the formulations of the magnesium alloy hollow nail body materials of each experimental group are shown in table 5, and the preparation method and conditions are referred to in example 1.
Table 5 Material formulation of magnesium alloy hollow nail body of each experimental group
(2) The magnesium alloy hollow nail body material of the experimental group 4-7 is used for testing the mechanical property (tensile strength and ductility) and the electrochemical property (open circuit potential), and the testing method comprises the following steps: an open circuit potential measurement method for evaluating long-term corrosion behavior of metal implant materials and medical instruments by referring to a GB/T228.1 metal material tensile test part 1, a room temperature test method YY/T1552-2017 surgical implant; inductively coupled plasma emission spectrometry (ICP-OES) analysis was performed on the elemental content of magnesium alloy.
(3) In order to evaluate the corrosion performance of the material, in-vitro degradation weightlessness experiments are carried out on magnesium alloy hollow nail body samples of the experimental group 4 and the experimental group 6, and according to the ASTMG1-03 standard, the corrosion rate is calculated according to the following formula:
corrosion rate = (kxw)/(axt x D)
Wherein k=8.76×10 4 W is the weight loss (g), A is the sample surface area (cm 2 ) T is soaking time (h), D is sample density (g/cm) 3 )。
2. Experimental results and analysis
(1) As can be seen from the results in Table 6, the change of the Ca content of the alloy has no significant effect on the tensile strength of the material, but has a significant effect on the elongation, and the elongation of the material suitable for clinical set screws is generally not less than 10%, so that both Mg-2Ca-1Zn and Mg-4Ca-1Zn can meet the requirements, and Mg-2Ca-1Zn is more ideal as a set screw processing material.
The corrosion resistance of the material is analyzed, and as the Ca proportion is increased, the open-circuit potential of the alloy is gradually reduced, so that the corrosion resistance is weakened, and the electrochemical angles also prove that the Mg-2Ca-1Zn and the Mg-4Ca-1Zn have good corrosion resistance potential.
TABLE 6 mechanical and electrochemical Properties of magnesium alloy materials
| Alloy composition | Tensile Strength/Mpa | Elongation percentage% | Open circuit potential/V |
| Experiment group 4 | 301.1 | 15.93 | -1.51 |
| Experiment group 5 | 326.0 | 5.33 | -1.62 |
| Experiment group 6 | 304.4 | 9.53 | -0.44 |
| Experiment group 7 | 303.4 | 5.31 | -1.77 |
(2) The results in table 7 show that the ratio of each alloy element is in the control range, the main impurities in the alloy are two elements of Al and Fe, the other impurities are all <0.0001, the table does not show, and the total impurity content is controlled in the range of < 0.1%. The materials of the experimental group 4 (Mg-2 Ca-1 Zn) and the experimental group 6 (Mg-4 Ca-1 Zn) are ideal magnesium alloy implant materials according to the physical property analysis of the materials.
TABLE 7 analysis of elemental content of magnesium alloy
(3) The results of the 130-day weightlessness experiment of the magnesium alloy hollow nail body (or the magnesium alloy guide pin) which is not subjected to the coating treatment are shown in table 8, and the corrosion appearance is shown in fig. 4.
As shown by the results of the preliminary material degradation test, the corrosion rates of Mg4CaZn and Mg2CaZn are slow, wherein the corrosion rate of Mg4CaZn is slower, and the corrosion rate corresponds to the magnitude of the open circuit potential of the material.
Based on all the experimental results, the magnesium alloy hollow nail bodies of the experimental group 4 (Mg 2 CaZn) and the experimental group 6 (Mg 4 CaZn) have better corrosion resistance, and the magnesium alloy hollow nail bodies of the experimental group 4 (Mg 2 CaZn) have higher elongation percentage and good corrosion resistance effect, so that the subsequent examples take the magnesium alloy hollow nail bodies of the Mg2Ca1Zn as targets for further experiments.
TABLE 8 untreated alloy weight loss test results
Example 5 optimization of inorganic ceramic coating
The magnesium alloy hollow nail body prepared in the experimental group 4 (Mg-2 Ca-1 Zn) of the example 2 is taken as an object to process a biological ceramic coating, the magnesium alloy hollow nail is prepared, the micro-arc oxidation applied voltage parameter is optimized, and the influence of voltage, frequency and duty ratio on the thickness, roughness and calcium element content of the coating is explored.
1. Influence of voltage on the coating
(1) Experiment and test method
The method of processing the bioceramic coating of this example was operated with reference to the procedure of experimental group 1 of example 1. The forward voltage of the micro-arc oxidation treatment is set as a variable, and the influence of the change of the forward voltage on the thickness of the coating, the content of calcium and the surface roughness of the magnesium alloy hollow nail is analyzed.
(2) Experimental results and analysis
As shown in the test result in FIG. 5, as the voltage increases, the thickness and the calcium content of the biological ceramic coating of the magnesium alloy hollow nail gradually increase, and the surface roughness of the magnesium alloy hollow nail is better about 380V, so that the subsequent micro-arc oxidation condition optimization experiment is carried out by adopting the forward voltage of 380-420V.
2. Parameter testing of micro-arc oxidation process
(1) The experimental method comprises the following steps:
according to the pre-experiment, the range of the surface coating research technological parameters is confirmed, the specific set research parameters are shown in table 9, and micro-arc oxidation experiments are respectively carried out on three magnesium alloy materials composed of different elements according to the parameter settings (the specific operation method is as shown in example 1), wherein the three magnesium alloy materials are Mg2CaZn alloy, EZ30 magnesium alloy and WE43 magnesium alloy respectively.
TABLE 9 setting of micro-arc oxidation parameters
(2) The testing method comprises the following steps:
A. the method for testing and evaluating the degradation rate of the surface coating parameters of the material comprises the following steps:
and respectively soaking the prepared samples (phi 16mm and 3 mm) subjected to micro-arc oxidation parameter exploration into a 3.5% NaCl solution until the samples are taken out after 180 days, washing surface degradation products with clear water, and evaluating the corrosion condition of the coating after airing.
B. In vitro degradation weight loss experiment: referring to the method of example 2, the Mg2CaZn alloy and Mg4CaZn alloy materials after the inorganic ceramic coating processing were subjected to the test after 120 days of treatment.
(3) Experimental results and analysis
(1) Evaluation based on the coating corrosion results of the materials of fig. 6 shows that the optimum parameters of the micro-arc oxidation process are set as follows: the voltage is 400V, the frequency is 1000Hz, the duty ratio is 10%, and the processing time is 10min; and the corrosion resistance of the coating of the Mg2CaZn alloy is optimal.
(2) As can be seen from the results of the 120-day in vitro degradation weightlessness experiment in comprehensive analysis table 10, the magnesium alloy hollow nail body material (Mg 2 CaZn) of the experimental group 1) in example 1 has lower degradation corrosion rate and is more corrosion resistant after surface treatment.
Table 10 results of the alloy weight loss experiments after the addition of the coating
Example 6 determination of physical Properties of magnesium alloy hollow nails
1. Experimental method
The magnesium alloy hollow nail body of experiment group 1 of example 1 was observed by a scanning electron microscope before and after the addition of the coating, and elemental analysis and second phase analysis in the alloy were performed.
2. Experimental results and analysis
(1) As shown in fig. 7 and 9, the magnesium alloy hollow nail body (or magnesium alloy bar) exhibits a typical dynamic recrystallization structure-fine equiaxed grains; the average grain size was measured by the intercept method as: 2.8.+ -. 0.3 μm. The grains are uniform and the particles are small, the material is uniform, and the particles are small to improve the corrosion resistance.
From the analysis of the results in FIG. 8, it is found that the ratio of Ca and Zn elements in the material structure is basically consistent with the design composition of the material; no significant inclusions and defects were seen in the tissue.
(2) Fig. 13 is a SEM characterization result of the through hole of the magnesium alloy hollow nail with or without the coating, and it is known from comparison of the graph that the inner surface of the through hole of the magnesium alloy hollow nail generates a uniform ceramic coating with a thickness of about 5-10um and the surface of the coating is in an uneven structure after the coating processing treatment.
FIG. 14 is an SEM image of the outer surface of the ceramic coating of a magnesium alloy hollow nail, from which it is seen that the micro-arc oxidized layer on the surface of the nail has a uniform texture and is flat, and can completely cover the surface of the magnesium alloy nail, and the surface of the layer is provided with uniformly distributed blind holes with a diameter of about 1-5um.
It will be understood that equivalents and modifications will occur to those skilled in the art in light of the present teachings and concepts, and all such modifications and substitutions are intended to be included within the scope of the present invention as defined in the accompanying claims.
Claims (10)
1. The magnesium alloy hollow nail is characterized by comprising a magnesium alloy hollow nail body and a layer of inorganic ceramic coating coated on the surface of the magnesium alloy hollow nail body; the magnesium alloy hollow nail body is provided with a through hole for a magnesium alloy guide pin to penetrate through along a central shaft, and the inorganic ceramic coating is also uniformly distributed on all inner surfaces of the through hole; the outer wall of the magnesium alloy hollow nail body is provided with threaded parts along the length direction; the self-corrosion potential of the inorganic ceramic coating is higher than that of the magnesium alloy hollow nail body.
2. The magnesium alloy hollow nail according to claim 1, wherein the screw thread part comprises a first screw thread part and a second screw thread part which are distributed on the outer side surface of the magnesium alloy body, and the two screw thread parts are adjacently arranged or are arranged at a certain distance; the outer end face of the head of the magnesium alloy hollow nail body is provided with a fastening groove.
3. The magnesium alloy hollow nail according to claim 1, wherein the magnesium alloy hollow nail body material comprises the following components in percentage by mass: 1.0-6.0% of Ca, 0.8-1.2% of Zn, less than 0.1% of impurity total amount and the balance of Mg.
4. The magnesium alloy hollow nail according to claim 1, wherein the inorganic ceramic coating is a micro-arc oxidation coating comprising the following elements in mass percent: 20-40% of Mg, 20-40% of O, 8-20% of P, 3-6% of Ca and 15-25% of F.
5. A magnesium alloy guide pin for being matched with the magnesium alloy hollow nail according to claim 1, which is characterized in that the magnesium alloy guide pin is of a rod-shaped structure, the outer diameter of the magnesium alloy guide pin is slightly smaller than the inner diameter of a through hole of the magnesium alloy hollow nail, and the length of the magnesium alloy guide pin is longer than the magnesium alloy hollow nail; the material of the magnesium alloy guide pin is the same as that of the magnesium alloy hollow nail body.
6. The method for preparing the magnesium alloy guide pin according to claim 5, wherein the method comprises the following steps: firstly, preparing a magnesium alloy bar, and processing the magnesium alloy bar into a magnesium alloy guide pin through a lathe; wherein the magnesium alloy bar comprises the following components in percentage by mass: 1.0-6.0% of Ca, 0.8-1.2% of Zn, less than 0.1% of impurity total amount and the balance of Mg.
7. The method for preparing the magnesium alloy hollow nail according to claim 1, comprising the steps of:
s1, preparing a magnesium alloy bar, and processing the magnesium alloy bar into a magnesium alloy hollow nail body through a lathe;
wherein the magnesium alloy bar comprises the following components in percentage by mass: 1.0 to 6.0 percent of Ca, 0.8 to 1.2 percent of Zn, less than 0.1 percent of impurity total amount and the balance of Mg;
s2, processing an inorganic ceramic coating on the surface of the magnesium alloy hollow nail body to obtain the magnesium alloy hollow nail.
8. The method for manufacturing a magnesium alloy hollow nail according to claim 7, wherein the method for manufacturing a magnesium alloy rod is as follows:
s11, melting pure magnesium at 750-800 ℃ under the protection of the atmosphere of the mixed protective gas, and preserving heat for 30-60 min; adding high-purity zinc and pure calcium with corresponding mass percentages, mechanically stirring for 3-5min, and preserving heat for 20-30 min; cooling to 700-730 ℃ and casting into cast ingots;
s12, performing a low-temperature extrusion molding process under the conditions that the extrusion ratio is 20-80, the extrusion temperature is 250-400 ℃ and the extrusion shaft speed is 0.1-1.0 mm/S, thereby obtaining the magnesium alloy bar.
9. The method for preparing a magnesium alloy hollow nail according to claim 7, wherein the method for processing the inorganic ceramic coating comprises the following steps:
s21, respectively weighing corresponding amounts of nano hydroxyapatite, glycol and triethanolamine, adding the nano hydroxyapatite, the glycol and the triethanolamine into water to prepare a solution A, and placing the solution A into an ultrasonic generator for ultrasonic assisted curing for 40-60min;
s22, weighing sodium hexametaphosphate and potassium fluoride dihydrate, and adding the sodium hexametaphosphate and the potassium fluoride dihydrate into water to prepare a solution B;
s23, slowly adding the solution A with the same volume into the solution B, and uniformly stirring to obtain a solution C;
s24, placing the cleaned magnesium alloy hollow nail body in a solution C to serve as an anode, and taking stainless steel as a cathode to perform micro-arc oxidation treatment;
s25, washing the magnesium alloy hollow nails obtained in the previous step with water and ethanol in sequence, and drying;
optionally, in the solution A, the mass concentration of the nano hydroxyapatite is 3-5g/L, the volume concentration of the ethylene glycol is 0.015-0.025%, and the volume concentration of the triethanolamine is 0.025-0.035%; in the solution B, the mass volume concentration of the sodium hexametaphosphate is 4-8g/L, and the mass volume concentration of the potassium fluoride dihydrate is 14-18g/L.
10. The use of the magnesium alloy hollow nail according to claim 1, characterized in that the application method is as follows: the magnesium alloy hollow nail and a magnesium alloy guide pin penetrating through the through hole are combined together for use; the two ends of the magnesium alloy guide pin are exposed outside the magnesium alloy guide pin, and the material of the magnesium alloy guide pin is the same as that of the magnesium alloy hollow nail body.
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