CN109537025B - Metal composite material containing corrosion-resistant coating, degradable magnesium alloy bone screw and application - Google Patents
Metal composite material containing corrosion-resistant coating, degradable magnesium alloy bone screw and application Download PDFInfo
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- CN109537025B CN109537025B CN201811569267.7A CN201811569267A CN109537025B CN 109537025 B CN109537025 B CN 109537025B CN 201811569267 A CN201811569267 A CN 201811569267A CN 109537025 B CN109537025 B CN 109537025B
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- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 111
- 238000005260 corrosion Methods 0.000 title claims abstract description 84
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 83
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 238000000576 coating method Methods 0.000 title claims abstract description 72
- 230000007797 corrosion Effects 0.000 title claims abstract description 63
- 239000002905 metal composite material Substances 0.000 title claims abstract description 35
- 238000004070 electrodeposition Methods 0.000 claims abstract description 69
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 53
- 239000000919 ceramic Substances 0.000 claims abstract description 36
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims abstract description 23
- 239000001506 calcium phosphate Substances 0.000 claims abstract description 22
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 22
- 235000011010 calcium phosphates Nutrition 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 230000008439 repair process Effects 0.000 claims abstract description 12
- 239000002131 composite material Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 238000011282 treatment Methods 0.000 claims description 55
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- 238000001035 drying Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 26
- 238000012545 processing Methods 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 24
- 239000012224 working solution Substances 0.000 claims description 24
- 229910045601 alloy Inorganic materials 0.000 claims description 18
- 239000000956 alloy Substances 0.000 claims description 18
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- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 claims description 12
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 12
- 239000004115 Sodium Silicate Substances 0.000 claims description 12
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 12
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 12
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 12
- 239000012266 salt solution Substances 0.000 claims description 12
- 235000010344 sodium nitrate Nutrition 0.000 claims description 12
- 239000004317 sodium nitrate Substances 0.000 claims description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 8
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- 210000001519 tissue Anatomy 0.000 abstract description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 13
- 230000001954 sterilising effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000009455 aseptic packaging Methods 0.000 description 10
- 238000007664 blowing Methods 0.000 description 10
- 230000004663 cell proliferation Effects 0.000 description 10
- 235000011187 glycerol Nutrition 0.000 description 10
- PEZBJHXXIFFJBI-UHFFFAOYSA-N ethanol;phosphoric acid Chemical compound CCO.OP(O)(O)=O PEZBJHXXIFFJBI-UHFFFAOYSA-N 0.000 description 9
- 238000000643 oven drying Methods 0.000 description 9
- 238000004506 ultrasonic cleaning Methods 0.000 description 9
- 238000001514 detection method Methods 0.000 description 8
- 229910052761 rare earth metal Inorganic materials 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 5
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- 238000010301 surface-oxidation reaction Methods 0.000 description 4
- 206010061218 Inflammation Diseases 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 230000004054 inflammatory process Effects 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 229910010293 ceramic material Inorganic materials 0.000 description 2
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- 229910001220 stainless steel Inorganic materials 0.000 description 2
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- 238000006467 substitution reaction Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 230000037314 wound repair Effects 0.000 description 2
- 208000010392 Bone Fractures Diseases 0.000 description 1
- 206010017076 Fracture Diseases 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 206010029350 Neurotoxicity Diseases 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 206010044221 Toxic encephalopathy Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 229920006237 degradable polymer Polymers 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- -1 stainless steel Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical group CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/30—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
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/024—Anodisation under pulsed or modulated current or potential
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Orthopedic Medicine & Surgery (AREA)
- Life Sciences & Earth Sciences (AREA)
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Abstract
The invention belongs to the field of medical instruments, and particularly relates to a metal composite material containing an anti-corrosion coating, a degradable magnesium alloy bone screw and application thereof. The metal composite material containing the anti-corrosion coating comprises a substrate and a composite coating attached to the substrate, wherein the composite coating comprises a ceramic oxide layer and a calcium phosphate layer from inside to outside in sequence, the ceramic oxide layer is attached to the substrate through micro-arc oxidation, and the calcium phosphate layer is attached to the ceramic oxide layer through electrochemical deposition. The metal composite material containing the corrosion-resistant coating improves the corrosion resistance and the tissue affinity of the metal material, is suitable for preparing bone repair materials, particularly bone internal fixation materials for bone repair, has the advantages of simple process, low cost, excellent performance, safety, environmental protection and easy implementation, and can smoothly implement industrialization. The invention also provides a degradable magnesium alloy bone screw prepared from the material.
Description
Technical Field
The invention belongs to the field of medical instruments, and particularly relates to a metal composite material containing an anti-corrosion coating, a degradable magnesium alloy bone screw and application thereof.
Background
Most of the early bone fixing nail materials for bone repair are made of inert metals, including stainless steel, titanium alloy, cobalt-based alloy and the like. The material has good strength and plasticity, and is beneficial to processing and forming. Meanwhile, the paint is not easy to corrode in human body, and can reduce the release of harmful ions. However, the elastic modulus of the traditional metal material is greatly different from that of human bone tissue, and a stress shielding effect is generated after the traditional metal material is implanted, so that the bone healing process is influenced or osteoporosis is caused; in addition, the inert metal material may release harmful ions after being implanted for a long time, and has the risks of causing inflammation and allergy, so that the inert metal material needs to be taken out after a secondary operation after bone healing, and the risk and the economic burden of a patient are increased. From the 20 th 50 s, degradable polymers and bioactive ceramic materials, which can be degraded in the human body to avoid secondary operations, have attracted attention, and have good biocompatibility and osteoinductivity. However, the mechanical strength of the high polymer bone fixing nail is low, the nail breakage often occurs in clinical use, and meanwhile, most of degradation products are acidic, so that the degradation products stimulate surrounding tissues and cause aseptic inflammation. And bioactive ceramic materials such as calcium phosphate salt and the like have low strength and high brittleness, and can only be used as fillers of bone defects and cannot be manufactured into bone fixing nails.
The magnesium alloy can be completely degraded in a human body, has elastic modulus, density and the like which are closer to human bones compared with other metal implant materials, can effectively avoid stress shielding effect, and has higher mechanical strength and good bone inductivity, so the magnesium alloy has good application potential as a bone repair material and is widely researched. Early studies show that magnesium alloy has good application prospect as a bone repair material, but the clinical application of the magnesium alloy also faces some challenges. In the early research, commercial magnesium alloy is mostly directly adopted, and Al element added in the alloy has chronic neurotoxicity; the rare earth elements are common alloy elements of magnesium alloy, can effectively improve the strength, heat resistance and corrosion resistance of the alloy (such as WE43), but part of the rare earth elements may have potential toxicity, and release of a large amount of rare earth elements poses potential threats to human health along with degradation of magnesium alloy implants in human bodies. The excessive degradation rate and severe local corrosion are another major challenge facing medical magnesium alloys. An excessively fast erosion rate generates a large amount of hydrogen, which accumulates around or under the implant and causes inflammation, affecting bone healing. Based on the problems, only a small amount of magnesium and magnesium alloy medical appliance products are on the market at present and are used for internal fixation treatment of fracture.
Disclosure of Invention
In order to overcome the disadvantages and drawbacks of the prior art, it is a primary object of the present invention to provide a metal composite with a corrosion-resistant coating, comprising a substrate and a ceramic oxide layer and a calcium phosphate layer attached to the surface of the substrate.
The invention also aims to provide a preparation method of the metal composite material containing the anti-corrosion coating, which is simple, convenient, clear, safe, environment-friendly and easy to implement and can smoothly implement industrialization.
It is a further object of the present invention to provide the use of the above metal composite material comprising a corrosion-resistant coating.
The fourth purpose of the invention is to provide a degradable magnesium alloy bone screw.
The invention is realized by the following technical scheme:
a metal composite material containing an anti-corrosion coating comprises a substrate and a composite coating attached to the substrate, wherein the composite coating comprises a ceramic oxide layer and a calcium phosphate layer from inside to outside in sequence;
the ceramic oxide layer is preferably attached to the substrate through micro-arc oxidation;
the calcium phosphate layer is attached to the ceramic oxide layer preferably by electrochemical deposition;
the substrate is stainless steel, titanium alloy, cobalt-based alloy, magnesium alloy or zinc alloy;
the substrate is preferably magnesium alloy;
the matrix is further preferably an extruded Mg-2Zn-0.5Y-1Nd-0.5Zr alloy, the rare earth content of the alloy is lower, and the safety risk of the alloy when a human body is implanted for a long time is far lower than that of WE43(Mg-4Y-3.4RE-0.7Zr) biological magnesium alloy;
the preparation method of the metal composite material containing the corrosion-resistant coating comprises the following steps:
(1) after being pretreated, the metal raw material is placed in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, and then is cleaned and dried to obtain a metal sample with an oxide ceramic layer attached to the surface;
(2) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (1) in an electrodeposition working solution for electrochemical deposition treatment, and then cleaning and drying to obtain a metal composite material containing an anti-corrosion coating;
the specific operation of the pretreatment in the step (1) is preferably:
ultrasonically cleaning a metal raw material in 0.1M sodium hydroxide solution, sequentially cleaning the metal raw material in pure water and absolute ethyl alcohol, drying, and electropolishing in phosphoric acid-ethyl alcohol solution;
the micro-arc oxidation electrolyte in the step (1) is a silicate system and comprises the following components in final concentration: 30-40 g/L of sodium silicate, 2-6 g/L of sodium hydroxide and 4-12 g/L of glycerol;
the specific conditions of the micro-arc oxidation treatment in the step (1) are preferably as follows:
the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 650-850 Hz, the duty ratio is 20-30%, the forward voltage is 340-280V, the reverse frequency is 500-600 Hz, the duty ratio is 15-25%, the reverse voltage is 60-50V, and the treatment time is 18-8 min;
the cleaning in the step (1) is preferably performed by pure water (namely, RO water);
the drying in the step (1) is preferably drying at 30-50 ℃;
the electrodeposition working solution in the step (2) is a mixed salt solution and comprises the following components in final concentration: 1.9-3.1 g/L of calcium nitrate tetrahydrate, 7.5-8.5 g/L of sodium nitrate, 0.5-1.0 g/L of ammonium dihydrogen phosphate and 8.5-11.5 ml/L of hydrogen peroxide;
the specific conditions of the electrodeposition treatment in the step (2) are preferably:
the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 10-14 Hz, the duty ratio is 8-12%, the forward voltage is 6-4V, the reverse frequency is 10-15 Hz, the duty ratio is 3-5%, the reverse voltage is 5-3V, and the treatment time is 35-25 min;
the cleaning in the step (2) is preferably performed by cleaning twice with pure water (i.e. RO water) and cleaning twice with high-purity water (i.e. ultra-pure water, UP water) in sequence;
the drying in the step (2) is preferably carried out by blowing and drying at 20-40 ℃ for 20-40 min;
the metal composite material containing the corrosion-resistant coating is applied to preparing bone repair materials;
the bone repair material is preferably an intraosseous fixing nail material for bone repair;
a degradable magnesium alloy bone screw is prepared from the metal composite material containing the corrosion-resistant coating;
the preparation method of the degradable magnesium alloy bone screw comprises the following steps:
processing a metal raw material into a bone screw, and then further processing according to the preparation method of the metal composite material containing the corrosion-resistant coating to obtain the degradable magnesium alloy bone screw;
the metal raw material is preferably processed into a bone screw by a multi-axis numerical control machining center;
the degradable magnesium alloy bone screw can be further sterilized and packaged;
the specific operation of sterilization and packaging is preferably high-temperature sterilization at 180 ℃ for 2h, and aseptic packaging is carried out;
the principle of the invention is as follows:
in order to solve the problems of low strength, high rare earth content, poor corrosion resistance and the like of the degradable metal material for bone repair in the prior art, the invention adopts the constant-pressure micro-arc oxidation technology to carry out magnesia ceramic modification on the surface of the metal matrix, improves the degradation resistance of the metal material and can meet the requirements of clinical treatment application; meanwhile, a calcium phosphate layer is prepared on the surface of the ceramic oxide layer by adopting a constant-voltage electrodeposition technology, on one hand, the fused pores on the surface of the ceramic oxide layer are sealed, so that the corrosion of body fluid to the matrix is reduced, and on the other hand, the calcium phosphate layer is favorable for improving the affinity of the metal matrix and bone tissues and promoting the wound repair of the bone tissues. The constant-voltage electrodeposition method reduces the agglomeration defect of calcium phosphate generated by the constant-current electrodeposition method, and is beneficial to the quality control of products.
Furthermore, the invention provides a degradable magnesium alloy bone screw which is obtained by further processing according to the preparation method of the metal composite material containing the anti-corrosion coating on the basis of processing bone screws by using metal raw materials, preferably by using the extruded Mg-2Zn-0.5Y-1Nd-0.5Zr alloy as a matrix, and the prepared degradable magnesium alloy bone screw has high strength and low rare earth content and contains the anti-corrosion coating
Compared with the prior art, the invention has the following advantages and effects:
(1) the invention solves the problems of low strength, high rare earth content, poor corrosion resistance and the like of the existing medical degradable metal material, and provides the metal composite material which has high strength and low rare earth content and contains the corrosion-resistant coating.
(2) The metal composite material containing the anti-corrosion coating comprises a substrate, and a ceramic oxide layer and a calcium phosphate layer which are attached to the surface of the substrate, so that the degradation resistance, the corrosion resistance and the tissue affinity of the material are improved, and the metal composite material is suitable for preparing a bone repair material, in particular an intraosseous fixing material for bone repair.
(3) The method has the advantages of simple process, low cost, excellent performance, safety, environmental protection, easy implementation and smooth implementation of industrialization.
(4) The degradable magnesium alloy bone screw provided by the invention adopts a constant-pressure micro-arc oxidation technology to carry out magnesium oxide ceramic modification on the surface of the magnesium alloy bone screw, so that the degradation resistance of the screw is improved, and the requirement of clinical treatment application of the bone screw can be met; the calcium phosphate layer is further prepared on the surface of the oxidized ceramic layer of the magnesium alloy bone screw by adopting a constant-voltage electrodeposition technology, on one hand, the fused pores on the surface of the oxidized ceramic layer are sealed, so that the corrosion of body fluid to the magnesium nail matrix is reduced, on the other hand, the calcium phosphate layer is favorable for improving the affinity of the magnesium nail and bone tissues and promoting the wound repair of the bone tissues, and the constant-voltage electrodeposition method reduces the calcium phosphate agglomeration defect generated by a constant-current electrodeposition method and is favorable for the quality control of products.
(5) The invention considers the requirements of human body implantation application on the mechanical property and the corrosion resistance of materials, fills the blank of the implementation aspect of the magnesium alloy human body implantation application, and can meet the requirements of human body bone tissues on the integrity and the mechanical property of the bone screws before healing.
Drawings
Fig. 1 is a product display diagram of a finished degradable magnesium alloy bone screw prepared in example 3.
FIG. 2 is a cross-sectional view of the ceramic oxide layer and the calcium phosphate layer on the surface of the degradable magnesium alloy bone screw prepared in example 3.
FIG. 3 is a scanning electron microscope image of the surface of the degradable magnesium alloy bone screw prepared in example 3; wherein, a: ceramic oxide layer, b: oxidizing the calcium phosphate layer on the ceramic layer.
FIG. 4 is a surface energy spectrum of a degradable magnesium alloy bone screw prepared in example 3; wherein, a: screw containing only oxide ceramic layer, b: screw comprising an oxide ceramic layer and a calcium phosphate layer.
Fig. 5 is a XRD pattern of the surface of the screw made in example 3, which contains only the oxide ceramic layer.
FIG. 6 is the XRD pattern of the surface of the degradable magnesium alloy bone screw prepared in example 3.
FIG. 7 is an analysis graph (Tafel plot) of the electrochemical test result of the degradable magnesium alloy bone screw manufactured in example 3; wherein, a: screw containing only oxide ceramic layer, b: screw c containing oxide ceramic layer and calcium phosphate layer: uncoated screws.
FIG. 8 is a graph showing the results of the cell proliferation rate of the leach liquor of the finished degradable magnesium alloy bone screw manufactured in example 3.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
The Mg-2Zn-0.5Y-1Nd-0.5Zr alloy described in the embodiment is disclosed in Chinese patent with the application number of '201310418031.4' and the application name of 'a degradable biomedical magnesium alloy and a preparation method thereof';
example 1
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 30g/L sodium silicate, 2g/L sodium hydroxide and 4g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the performance of the degradable magnesium alloy bone screw prepared by the embodiment is detected, and the method specifically comprises the following steps: the surface roughness of the surface of the degradable magnesium alloy bone screw is detected by a surface roughness tester (TRX180), the adhesion force of the coating is measured by a coating adhesion force automatic scratch tester (WS-2005), the thickness of the coating is measured by a metallographic microscope method (DM4M metallographic microscope), the hardness of the coating is measured by a microhardness method (HXD-1000 microhardness tester), the corrosion voltage, the corrosion current, the corrosion rate and the corrosion depth are measured by an electrochemical measuring method (RST5200F electrochemical workstation), the maximum torque is measured by a torsion testing machine (NDW-20), and the proliferation rate of L929 cells is measured by an MTT method (GBT 16886.5-2003) so as to evaluate the cytotoxicity and the biocompatibility.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.8552, coating adhesion 11.225N, coating thickness 14.354 mu m, coating microhardness 214.6HV, corrosion voltage-1.3717V and corrosion current 1.38E-08A/cm2Corrosion rate of 7.01E-05g/m2h, corrosion rate of 3.46E-04mm/y, phi 2.5 specification maximum torque of 0.41N.m, L929 cell proliferation rate>80％。
Example 2
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 40g/L sodium silicate, 6g/L sodium hydroxide and 12g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.7724, coating adhesion 15.718N, coating thickness 16.344 μm, coating microhardness 339.5HV, corrosion voltage-1.4486
V, corrosion current 8.14E-09A/cm2The corrosion rate is 3.52E-05g/m2h, corrosion rate of 1.74E-04mm/y, phi 2.5 specification maximum torque of 0.52N.m, L929 cell proliferation rate>80％。
Example 3
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) and (3) further sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at a high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw (figure 1), wherein figure 2 is a cross-sectional view of the surface oxidation ceramic layer and the calcium phosphate layer, figure 3 is a scanning electron microscope view of the surface oxidation ceramic layer and the calcium phosphate layer, figure 4 is a surface energy spectrum of the surface oxidation ceramic layer and the calcium phosphate layer, and figures 5 and 6 are XRD (X-ray diffraction) diagrams of the surface oxidation ceramic layer and the calcium phosphate layer.
The degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra1.1136, coating adhesion 17.73N, coating thickness 20.818 μm, coating microhardness 268.9HV, corrosion voltage-1.4458V and corrosion current 3.26E-08A/cm2The corrosion rate is 1.50E-04g/m2h, corrosion rate 7.43E-04mm/y (FIG. 7), phi 2.5 specification maximum torque 0.59N.m, L929 cell proliferation rate>80% (fig. 8).
Example 4
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 650Hz, the duty ratio is 20%, the forward voltage is 340V, the reverse frequency is 500Hz, the duty ratio is 15%, the reverse voltage is 60V, and the processing time is 18 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.7579, coating adhesion 19.16N, coating thickness 15.176 μm, coating microhardness 190.6HV, corrosion voltage-1.5618V, and corrosion current 2.54E-08A/cm2The corrosion rate is 1.18E-04g/m2h, corrosion rate of 5.83E-04mm/y, phi 2.5 specification maximum torque of 0.48N.m, L929 cell proliferation rate>80％。
Example 5
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 850Hz, the duty ratio is 30%, the forward voltage is 280V, the reverse frequency is 600Hz, the duty ratio is 25%, the reverse voltage is 50V, and the processing time is 8 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.8156, coating adhesion 6.528N, coating thickness 14.292 mu m, coating microhardness 219.9HV, corrosion voltage-1.5116V and corrosion current 4.55E-08A/cm2The corrosion rate is 1.88E-04g/m2h, corrosion rate of 9.93E-04mm/y, phi 2.5 specification maximum torque of 0.41N.m, L929 cell proliferation rate>80％。
Example 6
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin; the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 1.9g/L calcium nitrate tetrahydrate, 7.5g/L sodium nitrate, 0.5g/L ammonium dihydrogen phosphate and 8.5ml/L hydrogen peroxide, and the specific strips of the electrodeposition treatment are as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.6902, coating adhesion 9.93N, coating thickness 17.224 μm, coating microhardness 246.6HV, corrosion voltage-1.392V, and corrosion current 1.16E-08A/cm2The corrosion rate is 5.85E-05g/m2h, corrosion rate of 2.89E-04mm/y, phi 2.5 specification maximum torque of 0.58N.m, L929 cell proliferation rate>80％。
Example 7
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 3.1g/L calcium nitrate tetrahydrate, 8.5g/L sodium nitrate, 1.0g/L ammonium dihydrogen phosphate and 11.5ml/L hydrogen peroxide, and the specific strips of the electrodeposition treatment are as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 12Hz, the duty ratio is 10%, the forward voltage is 5V, the reverse frequency is 15Hz, the duty ratio is 4%, the reverse voltage is 4V, and the processing time is 30 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.7616, coating adhesion 3.828N, coating thickness 15.144 μm, coating microhardness 223.6HV, corrosion voltage-1.3759V, and corrosion current 2.84E-08A/cm2The corrosion rate is 1.07E-04g/m2h, corrosion rate of 5.31E-04mm/y, phi 2.5 specification maximum torque of 0.52N.m, L929 cell proliferation rate>80％。
Example 8
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 10Hz, the duty ratio is 8%, the forward voltage is 6V, the reverse frequency is 10Hz, the duty ratio is 3%, the reverse voltage is 5V, and the processing time is 35 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.784, coating adhesion 6.72N, coating thickness 13.932 μm, coating microhardness 252.9HV, corrosion voltage-1.3368V, and corrosion current 1.55E-08A/cm2The corrosion rate is 5.82E-05g/m2h, corrosion depth of 2.88E-04mm/y, phi 2.5 specification maximum torque of 0.45N.m, L929 cell proliferation rate>80％。
Example 9
(1) Mg-2Zn-0.5Y-1Nd-0.5Zr alloy is used as a metal raw material, a multi-axis numerical control machining center is adopted to machine a bone screw, and then the following pretreatment is carried out: ultrasonic cleaning with 0.1M sodium hydroxide solution, sequentially cleaning in pure water and anhydrous ethanol, oven drying at 45 deg.C, and electropolishing in phosphoric acid-ethanol solution;
(2) placing the metal raw material pretreated in the step (1) in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, wherein the micro-arc oxidation electrolyte is a silicate system and comprises the following components in final concentration: 35g/L sodium silicate, 4g/L sodium hydroxide and 8g/L glycerin, and the specific conditions of the micro-arc oxidation treatment are as follows: the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 750Hz, the duty ratio is 25%, the forward voltage is 310V, the reverse frequency is 550Hz, the duty ratio is 20%, the reverse voltage is 55V, and the processing time is 13 min; then, conventionally cleaning with pure water, and drying at 45 ℃ to obtain a metal sample with the surface attached with the oxide ceramic layer;
(3) and (3) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (2) into an electrodeposition working solution for electrodeposition treatment, wherein the electrodeposition working solution is a mixed salt solution and comprises the following components in final concentration: 2.5g/L calcium nitrate tetrahydrate, 8.0g/L sodium nitrate, 0.75g/L ammonium dihydrogen phosphate and 10ml/L hydrogen peroxide, and the specific strip of electrodeposition treatment is as follows: the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 14Hz, the duty ratio is 12%, the forward voltage is 4V, the reverse frequency is 15Hz, the duty ratio is 5%, the reverse voltage is 3V, and the processing time is 25 min; then, cleaning twice by using pure water conventionally, cleaning by using the pure water, and drying for 30min by blowing at normal temperature to obtain a metal composite material containing an anti-corrosion coating, namely the degradable magnesium alloy bone screw;
(4) sterilizing the degradable magnesium alloy bone screw prepared in the step (3) at high temperature of 180 ℃ for 2h, and carrying out aseptic packaging to obtain a finished product of the degradable magnesium alloy bone screw;
the degradable magnesium alloy bone screw prepared in the embodiment is subjected to performance detection, and the specific method is shown in embodiment 1.
The degradable magnesium alloy bone screw prepared by the embodiment has the following performance parameters: roughness Ra0.8218, coating adhesion 9.978N, coating thickness 15.922 mu m, coating microhardness 228.6HV, corrosion voltage-1.3413V and corrosion current 1.56E-08A/cm2Corrosion rate 7.89E-05g/m2h, corrosion rate of 3.90E-04mm/y, phi 2.5 specification maximum torque of 0.5N.m, L929 cell proliferation rate>80％。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A metal composite material containing an anti-corrosion coating is characterized by consisting of a substrate and a composite coating attached to the substrate, wherein the composite coating comprises a ceramic oxide layer and a calcium phosphate layer from inside to outside in sequence; the ceramic oxide layer is attached to the substrate through micro-arc oxidation; the calcium phosphate layer is attached to the ceramic oxide layer through electrochemical deposition; the matrix is Mg-2Zn-0.5Y-1Nd-0.5Zr alloy or zinc alloy;
the preparation method of the metal composite material containing the corrosion-resistant coating comprises the following steps:
(1) after being pretreated, the metal raw material is placed in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, and then is cleaned and dried to obtain a metal sample with an oxide ceramic layer attached to the surface;
(2) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (1) in an electrodeposition working solution for electrochemical deposition treatment, cleaning and drying to obtain a metal composite material containing the corrosion-resistant coating;
the micro-arc oxidation electrolyte in the step (1) is a silicate system and consists of the following components in final concentration: 30-40 g/L of sodium silicate, 2-6 g/L of sodium hydroxide and 4-12 g/L of glycerol;
the specific conditions of the micro-arc oxidation treatment in the step (1) are as follows:
the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 650-850 Hz, the duty ratio is 20-25%, the forward voltage is 340-280V, the reverse frequency is 500-600 Hz, the duty ratio is 15-25%, the reverse voltage is 60-50V, and the processing time is 18-8 min;
the electrodeposition working solution in the step (2) is a mixed salt solution and consists of the following components in final concentration: 1.9-2.5 g/L of calcium nitrate tetrahydrate, 7.5-8.5 g/L of sodium nitrate, 0.75-1.0 g/L of ammonium dihydrogen phosphate and 8.5-11.5 ml/L of hydrogen peroxide;
the specific conditions of the electrodeposition treatment in the step (2) are as follows:
the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 10-14 Hz, the duty ratio is 8-12%, the forward voltage is 6-4V, the reverse frequency is 10-15 Hz, the duty ratio is 3-5%, the reverse voltage is 5-3V, and the treatment time is 35-25 min.
2. The process for preparing a metal composite material containing a corrosion-resistant coating according to claim 1, characterized by comprising the steps of:
(1) after being pretreated, the metal raw material is placed in a micro-arc oxidation electrolyte for micro-arc oxidation treatment, and then is cleaned and dried to obtain a metal sample with an oxide ceramic layer attached to the surface;
(2) placing the metal sample with the surface attached with the ceramic oxide layer prepared in the step (1) in an electrodeposition working solution for electrochemical deposition treatment, cleaning and drying to obtain a metal composite material containing the corrosion-resistant coating;
the micro-arc oxidation electrolyte in the step (1) is a silicate system and consists of the following components in final concentration: 30-40 g/L of sodium silicate, 2-6 g/L of sodium hydroxide and 4-12 g/L of glycerol;
the specific conditions of the micro-arc oxidation treatment in the step (1) are as follows:
the constant voltage mode of the bidirectional pulse high-voltage power supply is adopted, and the electrical parameters are as follows: the forward frequency is 650-850 Hz, the duty ratio is 20-25%, the forward voltage is 340-280V, the reverse frequency is 500-600 Hz, the duty ratio is 15-25%, the reverse voltage is 60-50V, and the processing time is 18-8 min;
the electrodeposition working solution in the step (2) is a mixed salt solution and consists of the following components in final concentration: 1.9-2.5 g/L of calcium nitrate tetrahydrate, 7.5-8.5 g/L of sodium nitrate, 0.75-1.0 g/L of ammonium dihydrogen phosphate and 8.5-11.5 ml/L of hydrogen peroxide;
the specific conditions of the electrodeposition treatment in the step (2) are as follows:
the constant voltage mode of the bidirectional pulse power supply is adopted, and the bidirectional pulse electrodeposition parameters are as follows: the forward frequency is 10-14 Hz, the duty ratio is 8-12%, the forward voltage is 6-4V, the reverse frequency is 10-15 Hz, the duty ratio is 3-5%, the reverse voltage is 5-3V, and the treatment time is 35-25 min.
3. Use of a metal composite material comprising a corrosion-resistant coating according to claim 1 for the preparation of a bone repair material.
4. A degradable magnesium alloy bone screw, characterized in that it is made of the metal composite material containing corrosion-resistant coating as claimed in claim 1.
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