CN113249763A - Method for compounding tin dioxide electroactive bioceramic coating on surface of micro-arc magnesium oxide - Google Patents
Method for compounding tin dioxide electroactive bioceramic coating on surface of micro-arc magnesium oxide Download PDFInfo
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- CN113249763A CN113249763A CN202110514185.8A CN202110514185A CN113249763A CN 113249763 A CN113249763 A CN 113249763A CN 202110514185 A CN202110514185 A CN 202110514185A CN 113249763 A CN113249763 A CN 113249763A
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 239000011248 coating agent Substances 0.000 title claims abstract description 80
- 238000000576 coating method Methods 0.000 title claims abstract description 80
- 239000003462 bioceramic Substances 0.000 title claims abstract description 45
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 44
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 44
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000013329 compounding Methods 0.000 title claims abstract description 18
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 70
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000011777 magnesium Substances 0.000 claims abstract description 48
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 239000010410 layer Substances 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 239000010935 stainless steel Substances 0.000 claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 15
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000002344 surface layer Substances 0.000 claims abstract description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- 239000011259 mixed solution Substances 0.000 claims description 37
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000010335 hydrothermal treatment Methods 0.000 claims description 23
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 21
- 229910001868 water Inorganic materials 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 7
- 229910019400 Mg—Li Inorganic materials 0.000 claims description 6
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 4
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 4
- 229940079864 sodium stannate Drugs 0.000 claims description 4
- 239000001119 stannous chloride Substances 0.000 claims description 4
- 235000011150 stannous chloride Nutrition 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910020489 SiO3 Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052586 apatite Inorganic materials 0.000 abstract description 9
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[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 VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 abstract description 9
- 239000012890 simulated body fluid Substances 0.000 abstract description 8
- 230000000975 bioactive effect Effects 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 4
- 238000012986 modification Methods 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 238000005524 ceramic coating Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000000956 alloy Substances 0.000 description 5
- 210000000988 bone and bone Anatomy 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007943 implant Substances 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000004071 biological effect Effects 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 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 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- SPAGIJMPHSUYSE-UHFFFAOYSA-N Magnesium peroxide Chemical group [Mg+2].[O-][O-] SPAGIJMPHSUYSE-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000002138 osteoinductive effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 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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- A61L27/02—Inorganic materials
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- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/28—Materials for coating prostheses
- A61L27/30—Inorganic materials
- A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/54—Biologically active materials, e.g. therapeutic substances
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a method for compounding a tin dioxide electroactive bioceramic coating on a micro-arc magnesium oxide surface, and relates to the technical field of metal surface modification. The method comprises the following specific steps: placing the magnesium sample in a stainless steel tank filled with electrolyte for micro-arc oxidation; and placing the prepared micro-arc magnesium oxide sample in a reaction kettle to hydrothermally grow the nano granular tin dioxide. The obtained bioactive bioceramic coating has the following structural and performance characteristics: the coating is a double-layer composite coating, the inner layer is magnesium oxide and is in a micro-porous structure, and the surface layer is tin dioxide and is in a nano-particle shape. The coating structure has no discontinuous interface with the substrate, can rapidly induce and form bone-like apatite in a simulated body fluid environment, and has good bioactivity.
Description
Technical Field
The invention belongs to the technical field of metal surface modification, and particularly relates to a method for compounding a tin dioxide electroactive bioceramic coating on a micro-arc magnesium oxide surface.
Background
Magnesium and magnesium alloy are widely used as medical implant materials, but magnesium and magnesium alloy are biologically inert in application and do not have osteoinductive capacity, for example, the polypyrrole calcium phosphate/magnesium oxide biological ceramic coating and the preparation method thereof disclosed in the Chinese patent CN102304746A relate to a magnesium alloy surface ceramic coating and the preparation method thereof, and the polypyrrole calcium phosphate/magnesium oxide biological ceramic coating can be used for developing bone fixing materials such as magnesium-based bone plates, bone nails and the like; the micro-arc oxidation technology is a common magnesium surface bioactivity modification method, and can generate a magnesium oxide ceramic coating with a micro-porous structure on the surface of magnesium and magnesium alloy, but the coating prepared by the method has weaker bioactivity.
In the process of bone repair, the negative charge on the surface of the implant can promote the deposition of apatite and the expression of osteoblast, and is beneficial to the integration of bone tissues and the implant. By controlling the components of the solution, tin dioxide can grow on the surface of the metal oxide after hydrothermal treatment. For example, chinese patent CN111926365A discloses a magnesium alloy micro-arc oxidation efficient electromagnetic shielding coating and a preparation method thereof, wherein a mixed solution is used as a micro-arc oxidation electrolyte, a magnesium alloy workpiece subjected to pretreatment is used as an anode, and micro-arc oxidation treatment is performed to obtain a micro-arc oxidation coating containing carbonyl iron on the surface of the magnesium alloy.
As known, the heterogeneous P-N junction with the two-type structure formed by the layered composition of magnesium oxide and tin dioxide is beneficial to the separation of electrons and holes, so that the tin dioxide nano layer is enriched with electrons and has electronegativity to form a bioelectricity active coating. The biological activity of the surface coating of the magnesium and the alloy thereof prepared by the existing method is weaker.
Disclosure of Invention
The invention aims to provide a method for compounding a tin dioxide electroactive bioceramic coating on the surface of micro-arc magnesium oxide, which solves the problems in the background art by compounding a micro-arc oxidation coating with a porous structure and a tin dioxide nanoparticle layer to endow the coating with bioelectricity.
In order to solve the technical problems, the invention is realized by the following technical scheme:
the invention discloses a method for compounding a tin dioxide electroactive bioceramic coating on the surface of micro-arc magnesium oxide, which comprises the following steps:
step (1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; adding electrolyte into a stainless steel tank body by taking a magnesium sample as an anode, and placing the magnesium sample into the electrolyte for micro-arc oxidation by taking the stainless steel tank body as a cathode to obtain a micro-arc magnesium oxide sample;
step (2) hydrothermal treatment: adding tin salt, sodium hydroxide and absolute ethyl alcohol into deionized water to form a mixed solution, then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step (1) into the mixed solution, and performing hydrothermal treatment to obtain the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide.
Further, the parameters for performing the micro-arc oxidation in the step (1) are as follows:
the micro-arc oxidation adopts pulse voltage: the positive voltage is 250-450V, and the negative voltage is 0-100V;
the micro-arc oxidation pulse frequency is 200-800 Hz;
the pulse current width of the micro-arc oxidation is 100-1000 us;
and the micro-arc oxidation time is 5-15 min.
Further, the magnesium sample in the step (1) is pure magnesium, Mg-Zn, Mg-6Zn or Mg-Li magnesium alloy.
Further, in the step (1), the magnesium sample is placed in an electrolyte at 15-30 ℃ for micro-arc oxidation.
Further, the concentration of KOH in the electrolyte in the step (1) is 1-10 g/L, and Na2SiO3The concentration of (b) is 5-20 g/L.
Further, the concentration of tin salt in the mixed solution in the step (2) is 0.05-0.5 mol/L, and the concentration of sodium hydroxide is 0.02-1 mol/L; the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution in the step (2) is (1-5): 1.
Further, in the step (2), the tin salt is stannic chloride, stannous chloride or sodium stannate.
Further, the conditions of hydrothermal treatment in the step (2) are as follows: carrying out hydrothermal treatment at 120-190 ℃ for 0.5-10 h.
Furthermore, the tin dioxide electroactive bioceramic coating prepared by the method is a double-layer composite coating with a micro-porous and nano-particle composite structure, the inner layer is magnesium oxide and is in a micro-porous structure, the surface layer is nano-particle tin dioxide, and the thickness of the layer is 50-500 nm.
The invention has the following beneficial effects:
1. according to the invention, through two steps of treatment of micro-arc oxidation and hydrothermal treatment, the prepared bioelectricity active coating is a double-layer composite coating with a micro-porous and nano-particle composite structure, the inner layer is magnesium oxide, the surface layer is nano-particle tin dioxide, and a tin dioxide nano-particle layer generated by hydrothermal treatment is tightly combined with the micro-arc oxidation coating on the surface of magnesium without being influenced by the appearance of the porous structure;
2. the thickness of the tin dioxide nano-particle layer prepared by the method is between 50nm and 500nm, the expression of the electronegativity of the surface of a PN junction is facilitated, the biological activity of the magnesium alloy material can be obviously improved, and the generation of apatite can be observed on the surface of the magnesium alloy material after the simulated body fluid is soaked for 7 days;
3. according to the invention, a hydrothermal method is adopted to grow the tin dioxide nanoparticle layer on the surface of the magnesium oxide coating with the micro-porous structure to form the electroactive bioceramic coating, the process is simple, the cost is low, an incontinuous interface is not formed between the prepared coating and a substrate, the osteoid apatite can be quickly induced and formed in a simulated body fluid environment, and the bioactive bioceramic coating has good bioactivity; the magnesium alloy material subjected to surface modification is expected to be widely applied to the field of medical implants.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of a magnesium sample with an electroactive bioceramic coating prepared according to the present invention;
FIG. 2 is a surface macroscopic view of an electroactive bioceramic coating made in accordance with the present invention;
FIG. 3 is a surface macro-topography of an electroactive bioceramic coating made in accordance with the present invention;
FIG. 4 is a cross-sectional view of an electroactive bioceramic coating made in accordance with the present invention;
in the drawings, the components represented by the respective reference numerals are listed below:
a: magnesium matrix, B: magnesium oxide ceramic layer, C: a tin dioxide bioelectrically active coating.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "opening," "upper," "lower," "thickness," "top," "middle," "length," "inner," "periphery," "side," "end," "bottom," and the like are used in an orientation or positional relationship indicated for ease of description and simplicity of description, and do not indicate or imply that the referenced components or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus are not to be considered as limiting.
The invention discloses a method for compounding a tin dioxide electroactive bioceramic coating on the surface of micro-arc magnesium oxide, which comprises the following steps:
1)micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; the concentration of KOH in the electrolyte is 1-10 g/L, Na2SiO3The concentration of (A) is 5-20 g/L; the method comprises the following steps of taking a magnesium sample as an anode, adding electrolyte into a stainless steel tank body, taking the stainless steel tank body as a cathode, and placing the magnesium sample in the electrolyte at 15-30 ℃ for micro-arc oxidation, wherein the micro-arc oxidation parameters are as follows: the micro-arc oxidation adopts pulse voltage, the positive voltage is 250-450V, the negative voltage is 0-100V, the micro-arc oxidation pulse frequency is 200-800 Hz, the micro-arc oxidation pulse current width is 100-1000 us, and the micro-arc oxidation time is 5-15 min, so that a micro-arc magnesium oxide sample is obtained; wherein the magnesium sample is pure magnesium, Mg-Zn, Mg-6Zn or Mg-Li magnesium alloy;
2) hydrothermal treatment: adding tin salt, sodium hydroxide and alcohol into deionized water to form a mixed solution, wherein the concentration of the tin salt in the mixed solution is 0.05-0.5 mol/L, and the concentration of the sodium hydroxide is 0.02-1 mol/L; deionized water and absolute ethyl alcohol in the mixed solution according to the volume ratio of (1-5) to 1; then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step 1) in the mixed solution, and carrying out hydrothermal treatment at 120-190 ℃ for 0.5-10 h to obtain a tin dioxide electroactive bioceramic coating on the surface of magnesium; wherein the tin salt is stannic chloride, stannous chloride or sodium stannate.
The first embodiment is as follows:
1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; the concentration of KOH in the electrolyte is 1g/L, Na2SiO3The concentration of (A) is 20 g/L; the magnesium sample is taken as an anode, electrolyte is added into a stainless steel tank body, the stainless steel tank body is taken as a cathode, the magnesium sample is placed in the electrolyte at the temperature of 20 ℃ for micro-arc oxidation, and the micro-arc oxidation parameters are as follows: adopting pulse voltage for micro-arc oxidation, wherein the positive voltage is 350V, the negative voltage is 80V, the micro-arc oxidation pulse frequency is 500Hz, the micro-arc oxidation pulse current width is 200us, and the micro-arc oxidation time is 10min to obtain a micro-arc magnesium oxide sample; wherein the magnesium sample is pure magnesium;
2) hydrothermal treatment: adding tin salt, sodium hydroxide, water and alcohol into water to form a mixed solution, wherein the concentration of the tin salt in the mixed solution is 0.05mol/L, and the concentration of the sodium hydroxide is 0.5 mol/L; deionized water and absolute ethyl alcohol in the mixed solution according to the volume ratio of 2: 1; and then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step 1) in the mixed solution, and carrying out hydrothermal treatment at 160 ℃ for 5 hours to obtain the tin dioxide electroactive bioceramic coating on the surface of the magnesium. Wherein the tin salt is sodium stannate.
Fig. 1 is a schematic structural diagram of a magnesium sample with an electroactive bioceramic coating prepared in this embodiment, in which a coating prepared on a magnesium sample a by the method is a two-layer composite coating with a micro-porous and nanoparticle composite structure, an inner layer is magnesium dioxide B and is in a micro-porous structure, a surface layer is nanoparticle tin dioxide C, and a layer thickness is 100-1000 nm.
The ceramic coating generated by the pure magnesium sample with the bioactive bioceramic coating obtained in this example was observed by scanning electron microscopy, and the results are shown in fig. 2, 3 and 4: FIGS. 2 and 3 are photographs of the surface topography of the electro-active bioceramic coating according to the present embodiment, and it can be seen from FIGS. 2 and 3 that the coating is complete, the surface is covered with nanoparticles, and the micro-porous structure of the conventional micro-arc oxidation coating is provided; fig. 4 is a scanning electron microscope cross-sectional morphology photograph of the bioactive bioceramic coating in the embodiment, as can be seen from fig. 4, the coating is divided into two layers, there is no discontinuous interface between the layers, the thickness of the surface layer is about 200-500 nm, and after the magnesium sample with the bioactive bioceramic coating is soaked in simulated body fluid for 7 days, apatite can be generated on the surface.
Example two:
1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; the concentration of KOH in the electrolyte is 10g/L, Na2SiO3The concentration of (A) is 5 g/L; the magnesium sample is taken as an anode, electrolyte is added into a stainless steel tank body, the stainless steel tank body is taken as a cathode, the magnesium sample is placed in the electrolyte at the temperature of 20 ℃ for micro-arc oxidation, and the micro-arc oxidation parameters are as follows: the micro-arc oxidation adopts pulse voltage, the positive voltage is 400V, the negative voltage is 100V, the micro-arc oxidation pulse frequency is 400Hz, and the micro-arc oxidation pulse current width is 200us, and the micro-arc oxidation time is 15min, so as to obtain a micro-arc magnesium oxide sample; wherein the magnesium sample is Mg-Zn alloy;
2) hydrothermal treatment: adding tin salt, sodium hydroxide, water and alcohol into water to form a mixed solution, wherein the concentration of the tin salt in the mixed solution is 0.1mol/L, and the concentration of the sodium hydroxide is 1 mol/L; deionized water and absolute ethyl alcohol in the mixed solution according to the volume ratio of 4: 1; and then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step 1) in the mixed solution, and carrying out hydrothermal treatment at 190 ℃ for 0.5h to obtain the stannic oxide electroactive bioceramic coating on the surface of the magnesium. Wherein the tin salt is tin chloride;
when the ceramic coating generated by the Mg-Zn sample with the electroactive bioceramic coating obtained in the embodiment is observed by a scanning electron microscope, the coating is complete and has a double-layer structure, an discontinuous interface does not exist between layers, the surface has a micro-porous structure of a traditional micro-arc oxidation coating, the micro-porous structure is covered by nano particles, the thickness of the surface layer is about 200nm, and after the Mg-Zn sample with the electroactive bioceramic coating is soaked in simulated body fluid for 7 days, apatite can be generated on the surface of the sample.
Example three:
1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; the concentration of KOH in the electrolyte is 1g/L, Na2SiO3The concentration of (A) is 20 g/L; the magnesium sample is taken as an anode, electrolyte is added into a stainless steel tank body, the stainless steel tank body is taken as a cathode, the magnesium sample is placed in the electrolyte at the temperature of 10 ℃ for micro-arc oxidation, and the micro-arc oxidation parameters are as follows: adopting pulse voltage for micro-arc oxidation, wherein the positive voltage is 350V, the negative voltage is 70V, the micro-arc oxidation pulse frequency is 200Hz, the micro-arc oxidation pulse current width is 1000us, and the micro-arc oxidation time is 15min to obtain a micro-arc magnesium oxide sample; wherein the magnesium sample is Mg-6Zn alloy;
2) hydrothermal treatment: adding tin salt, sodium hydroxide, water and alcohol into water to form a mixed solution, wherein the concentration of the tin salt in the mixed solution is 0.3mol/L, and the concentration of the sodium hydroxide in the mixed solution is 0.7 mol/L; deionized water and absolute ethyl alcohol in the mixed solution according to the volume ratio of 5: 1; and then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step 1) in the mixed solution, and carrying out hydrothermal treatment at 160 ℃ for 10 hours to obtain the tin dioxide electroactive bioceramic coating on the surface of the magnesium. Wherein the tin salt is tin chloride.
When the ceramic coating generated by the Mg-6Zn sample with the electroactive bioceramic coating obtained in the embodiment is observed by a scanning electron microscope, the coating is complete and has a double-layer structure, an discontinuous interface does not exist between layers, the surface has a micro-porous structure of a traditional micro-arc oxidation coating, the micro-porous structure is covered by nano particles, the thickness of the surface layer is about 320nm, and after the Mg-6Zn sample with the electroactive bioceramic coating is soaked in simulated body fluid for 7 days, apatite can be generated on the surface of the sample.
Example four:
1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; the concentration of KOH in the electrolyte is 2g/L, Na2SiO3The concentration of (A) is 5 g/L; the magnesium sample is taken as an anode, electrolyte is added into a stainless steel tank body, the stainless steel tank body is taken as a cathode, the magnesium sample is placed in the electrolyte at 0 ℃ for micro-arc oxidation, and the micro-arc oxidation parameters are as follows: adopting pulse voltage for micro-arc oxidation, wherein the positive voltage is 250V, the negative voltage is 50V, the micro-arc oxidation pulse frequency is 800Hz, the micro-arc oxidation pulse current width is 100us, and the micro-arc oxidation time is 5min to obtain a micro-arc magnesium oxide sample; wherein the magnesium sample is Mg-Li alloy;
2) hydrothermal treatment: adding tin salt, sodium hydroxide, water and alcohol into water to form a mixed solution, wherein the concentration of the tin salt in the mixed solution is 0.5mol/L, and the concentration of the sodium hydroxide is 0.5 mol/L; deionized water and absolute ethyl alcohol in the mixed solution according to the volume ratio of 3: 1; and then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step 1) in the mixed solution, and carrying out hydrothermal treatment at 120 ℃ for 8h to obtain the tin dioxide electroactive bioceramic coating on the surface of the magnesium. Wherein the tin salt is stannous chloride.
When the ceramic coating generated by the Mg-Li sample with the electroactive bioceramic coating obtained in the embodiment is observed by a scanning electron microscope, the coating is complete and has a double-layer structure, an discontinuous interface does not exist between layers, the surface has a micro-porous structure of a traditional micro-arc oxidation coating and is covered by nano particles, the thickness of the surface layer is about 450nm, and after the Mg-Li sample with the electroactive bioceramic coating is soaked in simulated body fluid for 7 days, apatite can be generated on the surface of the sample.
A method for compounding a tin dioxide electroactive bioceramic coating on the surface of micro-arc magnesium oxide is characterized in that the electroactive bioceramic coating with a micro/nano composite structure is prepared by two steps of micro-arc oxidation and hydrothermal treatment, and the specific process is as follows: firstly, micro-arc oxidation of a sample is carried out, and a micro-porous structure micro-arc oxidation coating is generated on the surface of magnesium; secondly, carrying out hydrothermal treatment on the sample, growing tin dioxide nanoparticles on the surface of the micro-arc oxidation coating, and keeping the surface porous structure of the micro-arc oxidation coating; the bioelectricity-active coating prepared by the invention has a micron/nano composite structure, and a tin dioxide nano particle layer generated by hydrothermal reaction is tightly combined with the magnesium surface micro-arc oxidation coating, so that the coating is not influenced by the appearance of a porous structure; the thickness of the tin dioxide nano-particle layer prepared by the method is between 100nm and 1000nm, the expression of the electronegativity of the PN junction surface is facilitated, the biological activity of the material is obviously improved, and the generation of apatite can be observed on the surface of the material after the material is soaked in simulated body fluid for 7 days.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide is characterized by comprising the following steps of:
step (1) micro-arc oxidation treatment: KOH and Na2SiO3Adding into water to form electrolyte; adding electrolyte into a stainless steel tank body by taking a magnesium sample as an anode, and placing the magnesium sample into the electrolyte for micro-arc oxidation by taking the stainless steel tank body as a cathode to obtain a micro-arc magnesium oxide sample;
step (2) hydrothermal treatment: adding tin salt, sodium hydroxide and absolute ethyl alcohol into deionized water to form a mixed solution, then injecting the mixed solution into a hydrothermal reaction kettle, soaking the micro-arc magnesium oxide sample dried in the step (1) into the mixed solution, and performing hydrothermal treatment to obtain the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide.
2. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the parameters for micro-arc oxidation in the step (1) are as follows:
the micro-arc oxidation adopts pulse voltage: the positive voltage is 250-450V, and the negative voltage is 0-100V;
the micro-arc oxidation pulse frequency is 200-800 Hz;
the pulse current width of the micro-arc oxidation is 100-1000 us;
and the micro-arc oxidation time is 5-15 min.
3. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the magnesium sample in the step (1) is pure magnesium, Mg-Zn, Mg-6Zn or Mg-Li magnesium alloy.
4. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein in the step (1), the magnesium sample is placed in an electrolyte at 15-30 ℃ for micro-arc oxidation.
5. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the concentration of KOH in the electrolyte in the step (1) is 1-10 g/L, and Na is added2SiO3The concentration of (b) is 5-20 g/L.
6. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the method comprises the following steps:
the concentration of tin salt in the mixed solution in the step (2) is 0.05-0.5 mol/L, and the concentration of sodium hydroxide is 0.02-1 mol/L;
the volume ratio of the deionized water to the absolute ethyl alcohol in the mixed solution in the step (2) is (1-5): 1.
7. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the tin salt in the step (2) is tin chloride, stannous chloride or sodium stannate.
8. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the hydro-thermal treatment in the step (2) is performed under the following conditions: carrying out hydrothermal treatment at 120-190 ℃ for 0.5-10 h.
9. The method for compounding the tin dioxide electroactive bioceramic coating on the surface of the micro-arc magnesium oxide according to claim 1, wherein the tin dioxide electroactive bioceramic coating prepared by the method is a double-layer composite coating with a micro-porous and nano-particle composite structure, the inner layer is magnesium oxide and is in a micro-porous structure, the surface layer is nano-particle tin dioxide, and the thickness of the layer is 50-500 nm.
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