CN114921833B - Medical pure zinc material and preparation method and application thereof - Google Patents
Medical pure zinc material and preparation method and application thereof Download PDFInfo
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- CN114921833B CN114921833B CN202210666566.2A CN202210666566A CN114921833B CN 114921833 B CN114921833 B CN 114921833B CN 202210666566 A CN202210666566 A CN 202210666566A CN 114921833 B CN114921833 B CN 114921833B
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- 239000011701 zinc Substances 0.000 title claims abstract description 132
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 125
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000576 coating method Methods 0.000 claims abstract description 62
- 239000011248 coating agent Substances 0.000 claims abstract description 60
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 47
- 239000003792 electrolyte Substances 0.000 claims abstract description 28
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 17
- 229910000162 sodium phosphate Inorganic materials 0.000 claims abstract description 17
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000005238 degreasing Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007943 implant Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 abstract description 31
- 230000007797 corrosion Effects 0.000 abstract description 30
- 230000007547 defect Effects 0.000 abstract description 8
- 239000012567 medical material Substances 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000012620 biological material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 description 23
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000001736 Calcium glycerylphosphate Substances 0.000 description 2
- 229910001297 Zn alloy Inorganic materials 0.000 description 2
- 239000013060 biological fluid Substances 0.000 description 2
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 description 2
- 229940095618 calcium glycerophosphate Drugs 0.000 description 2
- 235000019299 calcium glycerylphosphate Nutrition 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- 229910007541 Zn O Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 210000002449 bone cell Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000018823 dietary intake Nutrition 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 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
- 230000004054 inflammatory process Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000057 systemic toxicity Toxicity 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 210000005167 vascular cell Anatomy 0.000 description 1
Classifications
-
- 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
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
Abstract
The invention relates to the field of medical materials, and discloses a medical pure zinc material, and a preparation method and application thereof. The surface of the pure zinc material is provided with a coating formed by micro-arc oxidation of sodium phosphate electrolyte, wherein the temperature of the sodium phosphate electrolyte is kept between 25 and 35 ℃ during micro-arc oxidation. The invention generates a coating on the surface of the pure zinc material through micro-arc oxidation, the coating has no defects such as cracks, holes and the like, the pores are uniformly distributed, the thickness of the film layer is moderate, the electrochemical impedance of the coating is high, the corrosion potential is increased, and the corrosion rate is reduced, thereby solving the problem that medical pure zinc is easy to corrode, and being more beneficial to the application of the pure zinc as a biological material.
Description
Technical Field
The invention relates to the field of medical materials, in particular to a medical pure zinc material, and a preparation method and application thereof.
Background
The degradable metal material is easy to be gradually degraded in physiological environment until completely disappeared due to high strength, good toughness, high bending fatigue strength and excellent mechanical processing property, and the degradation product has high biocompatibility and safety, can avoid secondary operation as an implantation material, can well solve the defects caused by the traditional inert metal implant, and is widely focused and studied in the aspect of cardiovascular and orthopedic diseases. Current research on degradable metal materials mainly includes magnesium-based metals, iron-based metals, and zinc-based metal materials. The biggest problem of magnesium-based metal materials is that the corrosion rate is too high, and the problems of premature degradation of mechanical support performance, excessive release of hydrogen, local basification and the like caused by excessive corrosion degradation are still to be solved. While the excellent mechanical properties of iron-based degradable metals can provide good mechanical support, the slow degradation rate and the problem of difficult degradation of corrosion products limit their further application.
The zinc-based degradable metal has better biocompatibility, obvious biological efficacy and standard potential between magnesium-based and iron-based metals, theoretically has more proper degradation and absorption rate, has great application potential in the field of intraosseous fixation implantation instruments, and gradually attracts attention of students. However, a key problem with zinc as a degradable metal is its local and systemic toxicity, since the recommended dietary intake of zinc is only 15-40 mg/day, for adultsThe whole body zinc content is only 2-3 g zinc. Zn in too high a concentration 2+ Has significant cytotoxicity in different cells, including human bone cells and vascular cells. Thus, study of control of Zn 2+ The sudden release from the implant has important significance for the application of zinc, and the regulation of the degradation speed of zinc alloy is also a key problem to be solved in the application of the material.
Disclosure of Invention
In view of the above, the present invention aims to provide a medical pure zinc material, which can improve the corrosion resistance of the pure zinc medical material and has good binding property with a pure zinc matrix, so as to prevent cytotoxicity caused by too fast degradation of the pure zinc material;
another object of the present invention is to provide a medical pure zinc material, which can improve the biological performance of the pure zinc medical material, so as to better interact with biological fluid;
another object of the present invention is to provide a method for preparing the above-mentioned medical pure zinc material and its application in preparing medical implants.
In order to solve the technical problems or at least partially solve the technical problems, the invention provides a method for solving the technical problems or at least partially solving the technical problems, and the invention provides a medical pure zinc material, wherein the surface of the medical pure zinc material is provided with a coating formed by micro-arc oxidation of sodium phosphate electrolyte; the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃ during micro-arc oxidation, and is lower than or exceeds the temperature range, so that the coating on the surface of the pure zinc material cannot smoothly appear, a large number of defects such as cracks and holes exist, and a large number of defects can fall off during cleaning; in still other embodiments of the present invention, the sodium phosphate electrolyte is subjected to micro-arc oxidation at a temperature of 30 ℃.
In certain embodiments of the invention, zn in the pure zinc material is more than or equal to 99.99%; in other embodiments of the present invention, the pure zinc material is No. 0 pure zinc, more specifically, the No. 0 pure zinc element composition (mass fraction) is: 0.001% of Al, 0.0003% of Mg, 0.001% of Fe, 0.003% of Cu, 0.0005% of Pb, 0.0001% of Cd, 0.0002% of Sn and more than or equal to 99.99% of Zn.
In certain embodiments of the invention, the concentration of the sodium phosphate electrolyte is 20 to 30g/L; in still other embodiments of the present invention, the sodium phosphate electrolyte has a concentration of 25g/L.
Meanwhile, the invention also provides a preparation method of the pure zinc material, which comprises the following steps:
step 1, polishing, degreasing and cleaning pretreatment of a pure zinc material;
and 2, taking the pretreated pure zinc material as an anode, and performing micro-arc oxidation in sodium phosphate electrolyte, wherein the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃. Wherein the time of the micro-arc oxidation can be selected according to the actual situation, in some embodiments of the present invention, the time of the micro-arc oxidation is 4-6min, and in other embodiments, the time of the micro-arc oxidation is 5min.
In certain embodiments of the present invention, step 1 is:
the pure zinc material is polished step by step, ultrasonic cleaning is carried out by adopting acetone, absolute ethyl alcohol and water, and then oil removal and cleaning are carried out by adopting alkaline oil removal liquid. The silicon carbide sand paper with gradually increased marks is adopted for polishing step by step, and the polishing degree is bright, no obvious scratches exist on the surface, and the lines are consistent. The alkaline degreasing liquid is sodium hydroxide, and can be 10% sodium hydroxide solution.
In some embodiments of the invention, the micro-arc oxidation is performed in an alternating current constant voltage mode, and compared with a constant current mode, the constant voltage mode has larger instantaneous energy, and the prepared coating results show that the coating thickness is more uniform, the compactness is better, and the corrosion resistance is also better.
In other embodiments of the present invention, the positive voltage +30v to +60deg.V, the negative voltage-20v to-40v, the pulse frequency is fixed at 0.1-0.3 Hz, and the duty ratio is set at 70% -90%. In other embodiments of the present invention, in the ac constant voltage mode, the voltage boost starts from 0V, and increases every 2V successively until a preset value, and positive and negative voltages are performed synchronously; the voltage step down is completed quickly, for example, it can be turned off directly.
In certain embodiments of the invention, pure zinc material is used as the positive electrode, other suitable metals such as stainless steel are used as the negative electrode, and the distance between the positive electrode and the negative electrode is controlled to be 10cm; the temperature of the sodium phosphate electrolyte is controlled and maintained at 25-35 ℃ by an internal and external circulation refrigerating device.
The existing degradable zinc alloy used as medical implant has over-fast degradation rate and is easy to cause Zn in human body 2+ The excessive concentration of (2) causes cytotoxicity, generates inflammation to inhibit cell adhesion and growth, has negative effects on damaged tissue repair, and cannot provide long-term effective fixation support for damaged bone tissues. The invention generates a coating on the surface of the pure zinc material through micro-arc oxidation, the coating has no defects such as cracks, holes and the like, the pores are uniformly distributed, the thickness of the film layer is moderate, the electrochemical impedance of the coating is high, the corrosion potential is increased, and the corrosion rate is reduced, thereby solving the problem that medical pure zinc is easy to corrode. Based on these excellent technical effects, the invention proposes the application of the pure zinc material in preparing medical implants.
Compared with the prior art, the pure zinc material with higher corrosion resistance provided by the invention has at least the following advantages:
(1) The pure zinc material provided by the invention overcomes the defects of cracks, holes and the like of the micro-arc oxidation coating, the pores are uniformly distributed, the thickness of the film layer is moderate, the corrosion rate of the pure zinc material is obviously reduced, and the corrosion resistance of the pure zinc material is improved;
(2) The pure zinc material provided by the invention has a better wettability contact angle, and is more beneficial to the application of the pure zinc material as a biological material;
(3) The pure zinc material provided by the invention adopts an alternating current constant voltage control operation mode in the preparation process, and compared with a constant current mode, the mode has larger instantaneous energy, and the prepared coating result shows that the thickness of the coating is more uniform, the compactness is better and the corrosion resistance is also better;
(4) The pure zinc material provided by the invention has the characteristics of environmental protection, few preparation steps, simple operation and low cost.
Description of the drawings:
FIG. 1 is a flow chart of the micro-arc oxidation process for preparing the pure zinc material according to the present invention;
FIG. 2 shows SEM results, EDS results, metallographic cross-sections and corresponding line scans of the pure zinc material coating of the present invention; wherein (a) and (b) are SEM images of the coating at 1000, 2000 x, respectively; (c) - (e) EDS element mapping of Zn, O, P in the face scan of (a); (f) is an EDS image of the coating; (g) is a metallographic cross section of the coating; (h) is a line scan corresponding to (g);
FIG. 3 is a XRD phase composition diagram of a micro-arc oxidation coating of a pure zinc material of the present invention;
FIG. 4 is a FTIR detection chart showing the micro-arc oxidation coating of pure zinc material of the present invention;
FIG. 5 is an XPS test chart of a micro-arc oxidation coating of a pure zinc material of the present invention;
FIG. 6 is a graph showing the corrosion current density comparison of a micro-arc oxidized coating of a pure zinc material of the present invention with a pure zinc substrate;
FIG. 7 is a graph showing the impedance modulus comparison of a micro-arc oxidized coating of a pure zinc material of the present invention with a pure zinc substrate;
FIG. 8 is a graph showing the wettability contact angle comparison of a micro-arc oxidized coating of a pure zinc material of the present invention with a pure zinc substrate, (a) pure zinc substrate; (b) a coating;
FIG. 9 is a SEM image (. Times.1000, scale bar 10 μm) of a micro-arc oxidized coating of pure zinc material prepared in comparative example 1;
FIG. 10 is a graph showing the corrosion current density of micro-arc oxidation coatings of pure zinc material prepared at various constant currents (+5A, +7A, +9A) for the pure zinc material of comparative example 1;
FIG. 11 is a SEM image (x 1000, scale 10 μm; x 5000, scale 1 μm) showing various multiples of the micro-arc oxidation coating of pure zinc material prepared in comparative example 2;
FIG. 12 is a SEM image (x 1000, scale 10 μm; x 5000, scale 1 μm) of a micro-arc oxidation coating of a pure zinc material prepared in comparative example 3 at various temperatures (10 ℃, 50 ℃, 80 ℃).
The specific embodiment is as follows:
the invention discloses a medical pure zinc material, a preparation method and application thereof, and a person skilled in the art can properly improve the process parameters by referring to the content of the material. It is expressly noted that all such similar substitutions and modifications will be apparent to those skilled in the art, and are deemed to be included in the present invention. While the present invention has been described with respect to the preferred embodiments, it will be apparent to those skilled in the relevant art that the present invention can be practiced and practiced with modification and alteration of the pure zinc material and its preparation and use described herein, or with appropriate modifications and combinations thereof, without departing from the spirit, scope and spirit of the invention.
The invention specifically provides a preparation method of the pure zinc material and the pure zinc material prepared by the preparation method, which comprises the following steps:
1. pure zinc substrate pretreatment
Cutting, polishing and ultrasonic cleaning with solvent on pure zinc material;
2. ultrasonic degreasing
Immersing a bright and clean pure zinc material into alkaline degreasing liquid, carrying out ultrasonic cleaning, and drying;
3. preparing micro-arc oxidation electrolyte
Dissolving sodium phosphate into deionized water, and uniformly stirring to obtain micro-arc oxidation electrolyte;
4. micro-arc oxidation
Placing the pure zinc subjected to surface pretreatment into micro-arc oxidation electrolyte, wherein the pure zinc is connected with the positive electrode of a power supply and used as the positive electrode, and an electrolytic tank of stainless steel is connected with the negative electrode of the power supply and used as the negative electrode; opening the refrigerating device and controlling the temperature; adopting a micro-arc oxidation alternating current pulse power supply to start power supply, wherein positive and negative voltages are respectively +30V- +60deg.V, -20V-40V in a constant voltage mode, the pulse frequency is fixed to be 0.1-0.3 Hz, the duty ratio is set to be 70% -90%, and micro-arc oxidation is carried out to obtain a pure zinc material with a micro-arc oxidation coating on the surface;
5. post-plate treatment
All samples were rinsed with deionized water and dried at ambient temperature.
Unless specifically stated otherwise, the experimental environment and parameter conditions for each group in the test remained consistent, except for the differences explicitly noted.
The medical pure zinc material, the preparation method and the application thereof are further described below.
Example 1: preparation of the medical pure zinc material of the invention
1. Preparation method
1. Pure zinc substrate pretreatment
The pure zinc substrate is zinc No. 0, and the element components (mass fraction) thereof are as follows: 0.001% of Al, 0.0003% of Mg, 0.001% of Fe, 0.003% of Cu, 0.0005% of Pb, 0.0001% of Cd, 0.0002% of Sn and more than or equal to 99.99% of Zn. Dividing a pure zinc matrix into sizes of 25mm multiplied by 2mm by using linear cutting, then carrying out rough grinding by using 240# silicon carbide abrasive paper, removing obvious processing marks on the surface and periphery of a pure zinc matrix test piece, carrying out fine grinding by using 400# to 800# to 1000# to 2000# silicon carbide abrasive paper, enabling the fine grinding effect to reach the effect that the surface is bright, no obvious scratches and consistent lines, respectively carrying out ultrasonic cleaning in acetone, absolute ethyl alcohol and deionized water for 10min, and carrying out air drying by using an electric hair drier, thereby obtaining a pretreated pure zinc matrix;
2. ultrasonic degreasing
Immersing bright clean pure zinc into degreasing liquid, wherein the degreasing liquid is 10% sodium hydroxide solution, the temperature is 60 ℃, performing ultrasonic cleaning for 10min, taking out the pure zinc, cleaning the pure zinc with clear water for 3 times, and drying by using an electric hair drier to obtain a pure zinc matrix after ultrasonic treatment;
3. preparing micro-arc oxidation electrolyte
The formulation of the micro-arc oxidation electrolyte is 25g/L, the first step is to add 3L of deionized water into the electrolytic tank, the second step is to add 75g of sodium phosphate into the electrolytic tank, and the mixture is fully stirred until the sodium phosphate is completely dissolved, so as to obtain the micro-arc oxidation electrolyte. The micro-arc oxidation electrolyte needs to be replaced every time of micro-arc oxidation operation, and the micro-arc oxidation electrolyte prepared every time needs to be used within 24 hours to prevent the micro-arc oxidation electrolyte from deteriorating;
4. micro-arc oxidation
Placing the pure zinc subjected to surface pretreatment into micro-arc oxidation electrolyte, wherein the pure zinc is connected with the positive electrode of a power supply, the pure zinc is used as the positive electrode, an electrolytic tank of stainless steel is connected with the negative electrode of the power supply, and the pure zinc is used as the negative electrode, and the distance between the positive electrode and the negative electrode is controlled at 10cm; opening the refrigerating device, and controlling the temperature to be 30 ℃; the micro-arc oxidation alternating current pulse power supply is adopted to start power supply, the voltage is respectively +50V-30V in a constant voltage mode, the voltage boosting mode is that the voltage is gradually increased from 0V, positive and negative directions are synchronously carried out every 2V, the voltage reduction is fast, the operation can be directly closed, the pulse frequency is fixed to be 0.2Hz, the duty ratio is set to be 80%, the micro-arc oxidation time is 5min, and then pure zinc with a micro-arc oxidation coating on the surface is obtained;
5. post-plate treatment
All samples were rinsed with deionized water and dried at ambient temperature.
The flow chart of the micro-arc oxidation preparation of the pure zinc material is shown in figure 1.
2. Performance detection
Preparing a plurality of groups of samples by the same parameters according to the preparation process, carrying out SEM (scanning electron microscope) detection on one group of samples, and observing and characterizing the surface morphology and thickness of the coating; a set of samples were analyzed XRD, FTIR, XPS to demonstrate successful preparation of the corrosion resistant coating; a group of samples are used for carrying out electrochemical experiments to test the impedance modulus and the corrosion current density of the corrosion-resistant coating; the relevant test results are as follows;
1. an SEM image of the coating, elemental mapping of the face scan, EDS image, metallographic cross-section, and corresponding cross-section line scan are shown in fig. 2. As can be seen from fig. 2 a-b, the surface of the coating is uniformly distributed with micro-scale pores, and the surface is free of visible defects such as holes and cracks; as can be seen from c to f in fig. 2, elements such as O, zn, P and the like are uniformly distributed on the surface of the coating; as can be seen from g-f of FIG. 2, the thickness of the coating is 10-20 μm, and the characteristic curves of Zn, O and other elements have mutation, which shows that the coating has good bonding property with the substrate.
2. The XRD spectrum of the coating is shown in figure 3. It can be seen that the strong diffraction peaks found at 31.8 °, 34.6 °, 36.5 ° can be attributed to ZnO, zinc oxide being produced during micro-arc oxidation due to Zn produced when zinc is electrolyzed with water 2+ With O 2– /OH – The reaction between them. At the same time, the second order peaks corresponding to 47.1 °, 56.7 °, 63.1 °, 68.1 ° also confirm zinc oxideIs present. It follows that the coating is mainly composed of ZnO.
3. FTIR detection of the coating is shown in fig. 4. As can be seen from FIG. 4, at 433cm -1 The left and right show strong absorption peaks, which are the stretching vibration of Zn-O, indicating successful preparation of ZnO.
4. An XPS test of the micro-arc oxidized coating is shown in FIG. 5. As can be seen from fig. 5, the absorption peak of Zn, O, C, P corresponds to four distinct peaks. From XRD, FTIR and XPS results, it can be seen that the coating consists mainly of ZnO.
5. A graph of corrosion current density versus the coated pure zinc material versus the pure zinc substrate is shown in fig. 6. As can be seen from FIG. 6, the corrosion current density and corrosion potential of the pure zinc matrix were 21.810.+ -. 0.042. Mu.A/cm, respectively 2 and-1.078±0.013V; the corrosion current density and corrosion potential of the pure zinc material with the coating after micro-arc oxidation are respectively 0.562+/-0.050 mu A/cm 2 and-0.098±0.014V. This shows that the preparation of the coating significantly improves the corrosion resistance of the pure zinc material.
6. FIG. 7 shows a plot of the impedance modulus of the coating versus a pure zinc substrate. As can be seen from fig. 7, the coating exhibits a greater impedance modulus in both the low and high frequency regions, is more stable, and provides a better corrosion barrier to the protective substrate.
7. Fig. 8 shows a graph of the wettability contact angle of a coating with a pure zinc substrate, (a) being a pure zinc substrate; (b) is a coated pure zinc material. As can be seen from fig. 8, the wettability contact angle of the polished pure zinc substrate was about 87.4±1.0°, and the wettability contact angle of the coating layer was about 82.4±0.6°. The smaller wettability contact angle represents better biological performance, and compared with a pure zinc matrix, the pure zinc material with the coating can be better closely interacted with biological fluid.
Comparative example 1: preparation of pure zinc material in constant-current mode
Referring to the preparation procedure of example 1, the micro-arc oxidation was changed to constant current mode: +5- +9A, -3A;
scanning electron microscope (shown in figure 9) observes that uneven and non-compact coating is formed on the surface of the substrate, micropores are distributed on the surface of the coating, most places are corroded, the content of P element on the surface is small, and the binding force between the coating and the pure zinc substrate is poor. The results of electrochemical tests (as shown in fig. 10) show that the coating of this comparative example does not improve the corrosion performance of the pure zinc substrate, or even accelerate the corrosion thereof, compared to the self-corrosion potential of pure zinc as shown in fig. 6.
Comparative example 2: preparation of pure zinc material by calcium glycerophosphate electrolyte
Referring to the preparation procedure of example 1, the electrolyte was adjusted to other phosphates: 0.02mol/L calcium glycerophosphate;
scanning electron microscope (shown in figure 11) observes that uneven and non-compact coating is formed on the surface of the substrate, a large number of cracks are distributed on the surface of the coating, galvanic corrosion is formed between the substrate and the coating due to the existence of the large number of cracks, the corrosion of the substrate is accelerated, and the coating is easy to fall off. The coatings prepared in this comparative example are not suitable for improving the corrosion properties of the substrate.
Comparative example 3: preparation of pure zinc material by different electrolyte temperatures
Referring to the preparation process of example 1, the electrolyte temperatures were set at 10 ℃, 50 ℃ and 80 ℃, respectively;
scanning electron microscopy (shown in fig. 12) observes that the coating cannot be smoothly formed when the temperature of the substrate is too high or too low, and a large number of defects (cracks and holes) exist, so that the substrate can be largely detached during cleaning. This comparative example shows that temperature has a great influence on the coating formation in this example 1.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (7)
1. A medical pure zinc material is characterized in that a coating formed by micro-arc oxidation of 20-30 g/L sodium phosphate electrolyte is arranged on the surface of the pure zinc material; the temperature is kept at 25-35 ℃ during micro-arc oxidation of the sodium phosphate electrolyte, and the micro-arc oxidation is carried out in an alternating current constant voltage mode: positive voltage +30V- +60deg.V, negative voltage-20V-40V, pulse frequency is fixed to 0.1-0.3 Hz, and duty ratio is set to 70% -90%.
2. The pure zinc material according to claim 1, wherein the pure zinc material has a Zn content of 99.99% or more.
3. The pure zinc material of claim 1 or 2, wherein the pure zinc material is No. 0 zinc.
4. Use of a pure zinc material according to any one of claims 1 to 3 for the preparation of a medical implant.
5. The method for preparing the pure zinc material according to claim 1, which comprises the following steps:
step 1, polishing, degreasing and cleaning pretreatment of a pure zinc material;
2, taking the pretreated pure zinc material as an anode, and carrying out micro-arc oxidation on sodium phosphate electrolyte in an alternating current constant voltage mode, wherein the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃; in the alternating current constant voltage mode, positive voltage is +30V to +60deg.V, negative voltage is-20V to-40V, pulse frequency is fixed to be 0.1-0.3 Hz, and duty ratio is set to be 70% -90%.
6. The method according to claim 5, wherein step 1 is:
the pure zinc material is polished step by step, ultrasonic cleaning is carried out by adopting acetone, absolute ethyl alcohol and water, and then oil removal and cleaning are carried out by adopting alkaline oil removal liquid.
7. The method according to claim 5, wherein in the alternating current constant voltage mode, the voltage boost is started from 0V, and every 2V is gradually increased until a preset value, and positive and negative voltages are synchronously performed; the voltage step down is completed quickly.
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| CN107829123A (en) * | 2017-10-09 | 2018-03-23 | 深圳市中科摩方科技有限公司 | A kind of aluminium alloy of surface duplex coating and its preparation method and application |
| CN110241453A (en) * | 2019-04-25 | 2019-09-17 | 西南大学 | A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof |
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| CN107829123A (en) * | 2017-10-09 | 2018-03-23 | 深圳市中科摩方科技有限公司 | A kind of aluminium alloy of surface duplex coating and its preparation method and application |
| CN110241453A (en) * | 2019-04-25 | 2019-09-17 | 西南大学 | A kind of release fluoride and the degradable kirsite bone nail of cerium and preparation method thereof |
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| "不同工艺参数对微弧氧化医用纯锌表面微观组织和性能的影响";张昕等;《表面技术》;第50卷(第2期);第39-47页 * |
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