CN114921833A - 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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- CN114921833A CN114921833A CN202210666566.2A CN202210666566A CN114921833A CN 114921833 A CN114921833 A CN 114921833A CN 202210666566 A CN202210666566 A CN 202210666566A CN 114921833 A CN114921833 A CN 114921833A
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- 239000011701 zinc Substances 0.000 title claims abstract description 132
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 124
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 claims abstract description 64
- 239000011248 coating agent Substances 0.000 claims abstract description 61
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 50
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- 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
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000007943 implant Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 6
- 238000005238 degreasing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 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
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- 230000009286 beneficial effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 description 17
- 239000011159 matrix material Substances 0.000 description 13
- 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
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 5
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- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
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- 230000004048 modification Effects 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
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- 229910052742 iron Inorganic materials 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 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
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010061218 Inflammation Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
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Images
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 a sodium phosphate electrolyte, wherein the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃ during micro-arc oxidation. The invention generates the coating on the surface of the pure zinc material through micro-arc oxidation, the coating has no defects of cracks, holes and the like, the holes are uniformly distributed, the thickness of the coating 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 the medical pure zinc is easy to corrode and being more beneficial to the application of the medical 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 a physiological environment until completely disappeared due to high strength, good toughness, high bending fatigue strength and excellent machining performance, and the degradation product has high biocompatibility and safety, so that the degradable metal material can be used as an implant material to avoid a secondary operation, can well overcome the defects brought by the traditional inert metal implant, and is widely concerned and researched in the aspects of cardiovascular and orthopedic diseases. At present, the research on degradable metal materials mainly comprises magnesium-based metal, iron-based metal and zinc-based metal materials. The biggest problem of the magnesium-based metal material is that the corrosion rate is too fast, and the problems of premature decline of mechanical support performance, excessive release of hydrogen and local alkalization caused by too fast corrosion degradation still need to be solved. While for iron-based degradable metals, their excellent mechanical properties can provide good mechanical support, the slow degradation rate and the problem of difficult degradation of corrosion products limit their further applications.
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, shows great application potential in the field of intrabony fixing and implanting instruments, and gradually draws 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, and the adult systemic zinc content is also only 2-3 grams of zinc. Too high concentration of Zn 2+ Has significant cytotoxicity in different cells, including human bone cells and vascular cells. Therefore, investigation controls Zn 2+ The sudden release of the zinc from the implant has important significance for the application of zinc, and the regulation and control of the degradation speed of the zinc alloy also become a key difficult problem to be solved urgently 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, thereby preventing 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 closely;
the invention also aims to provide a preparation method of the medical pure zinc material and application of the medical pure zinc material in preparation of medical implants.
In order to solve the above technical problems or at least partially solve the above technical problems, the present invention provides a method for solving the above technical problems or at least partially solving the above technical problems, the present invention provides a medical pure zinc material having a coating layer formed by micro-arc oxidation of a sodium phosphate electrolyte on the surface thereof; when the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃ during micro-arc oxidation, the temperature is lower than or exceeds the temperature range, coatings on the surfaces of pure zinc materials cannot be smoothly generated, a large number of defects such as cracks, holes and the like exist, and a large number of defects drop off during cleaning; in other embodiments of the present invention, the temperature of the sodium phosphate electrolyte during micro-arc oxidation is 30 ℃.
In certain embodiments of the invention, Zn is greater than or equal to 99.99% in the pure zinc material; in other embodiments of the present invention, the pure zinc material is pure zinc No. 0, and more specifically, the elemental composition (mass fraction) of pure zinc No. 0 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 some embodiments of the invention, the concentration of the sodium phosphate electrolyte is 20-30 g/L; in other embodiments of the present invention, the concentration of the sodium phosphate electrolyte is 25 g/L.
Meanwhile, the invention also provides a preparation method of the pure zinc material, which comprises the following steps:
and 2, taking the pretreated pure zinc material as a positive electrode, and performing micro-arc oxidation in a sodium phosphate electrolyte, wherein the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃. The micro-arc oxidation time can be selected according to actual conditions, and in some embodiments of the invention, the micro-arc oxidation time is 4-6min, while in other embodiments, the micro-arc oxidation time is 5 min.
In certain embodiments of the invention, step 1 is:
polishing the pure zinc material step by step, carrying out ultrasonic cleaning by adopting acetone, absolute ethyl alcohol and water, and then removing oil and cleaning by adopting alkaline degreasing liquid. And the step-by-step polishing is performed by using silicon carbide abrasive paper with gradually increased marks, and the polishing degree is uniform until the surface is bright, has no obvious scratch and has consistent lines. The alkaline deoiling liquid is sodium hydroxide, and can be selected from 10% sodium hydroxide solution.
In some embodiments of the invention, the micro-arc oxidation is performed in an alternating current constant voltage mode, and the constant voltage mode has larger instantaneous energy compared with a constant current mode, and the prepared coating has the advantages of more uniform coating thickness, better compactness and higher corrosion resistance.
In other embodiments of the present invention, the AC constant voltage mode has a positive voltage of +30V to +60V, a negative voltage of-20V to-40V, a pulse frequency of 0.1 to 0.3Hz, and a duty ratio of 70 to 90%. In other embodiments of the present invention, in the ac constant voltage mode, the voltage boosting starts from 0V, and increases every 2V, until the preset value, the positive and negative voltages are synchronized; the voltage reduction is done quickly, e.g. it can be turned off directly.
In some embodiments of the present 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 10 cm; the temperature of the sodium phosphate electrolyte is controlled and kept at 25-35 ℃ by an internal and external circulation refrigerating device.
The existing degradable zinc alloy used as a medical implant has too high degradation rate and is easy to cause Zn of a human body 2+ The high concentration of the (B) can cause cytotoxicity, generate inflammation to inhibit cell adhesion and growth, generate negative effects on damaged tissue repair, and can not provide long-term effective fixed support for damaged bone tissues. The invention generates the coating on the surface of the pure zinc material through micro-arc oxidation, the coating has no defects of cracks, holes and the like, the holes are uniformly distributed, the thickness of the coating 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 the medical pure zinc is easy to corrode. Based on the excellent technical effects, the invention provides the application of the pure zinc material in the preparation of medical implants.
Compared with the prior art, the pure zinc material with higher corrosion resistance provided by the invention at least has the following advantages:
(1) the pure zinc material provided by the invention makes up the defects of cracks, holes and the like of the micro-arc oxidation coating, the holes 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 favorable for application as a biological material;
(3) compared with a constant-current mode, the mode has larger instantaneous energy, and the prepared coating has the advantages that the thickness of the coating is more uniform, the compactness is better, and the coating is more corrosion-resistant;
(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;
FIG. 2 shows SEM results, EDS results, metallographic cross-sections and corresponding line scans of the pure zinc material coating according to the invention; wherein (a) and (b) are 1000, 2000 times SEM images of the coating, respectively; (c) - (e) EDS element mapping of Zn, O, P in the face scan of (a); (f) EDS image for the coating; (g) is the metallographic cross section of the coating; (h) is (g) a corresponding line scan;
FIG. 3 is an XRD phase composition diagram of the micro-arc oxidation coating of pure zinc material according to the present invention;
FIG. 4 is an FTIR detection of a micro-arc oxidation coating of pure zinc material of the present invention;
FIG. 5 is an XPS test of a micro-arc oxidation coating of pure zinc material of the present invention;
FIG. 6 is a graph showing the comparison of the corrosion current density of the micro-arc oxidation coating of pure zinc material and pure zinc matrix according to the present invention;
FIG. 7 is a graph showing the comparison of the resistance modulus of the micro-arc oxidation coating of pure zinc material of the present invention and a pure zinc substrate;
FIG. 8 is a graph showing a comparison of wettability contact angles of a micro-arc oxidation coating and a pure zinc matrix of a pure zinc material according to the present invention, (a) a pure zinc substrate; (b) coating;
FIG. 9 is an SEM image (x 1000, scale 10 μm) of the micro-arc oxidation coating of pure zinc material prepared in comparative example 1;
FIG. 10 is a graph showing the corrosion current density of the micro-arc oxidation coatings of the pure zinc material prepared under different constant currents (+5A, +7A, +9A) for the pure zinc material of comparative example 1;
FIG. 11 is SEM images (x 1000, 10 μm scale; x 5000, 1 μm scale) of different multiples of the micro-arc oxidation coating of pure zinc material prepared in comparative example 2;
FIG. 12 shows SEM images (x 1000, 10 μm; x 5000, 1 μm) of micro-arc oxidized coatings of pure zinc material prepared in comparative example 3 at different temperatures (10 ℃, 50 ℃, 80 ℃).
The specific implementation mode 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 realize the medical pure zinc material by properly improving process parameters by referring to the content. It is specifically noted that all such substitutions and modifications will be apparent to those skilled in the art and are intended to be included herein. While the pure zinc materials and methods of making and using the same of the present invention have been described in terms of preferred embodiments, it will be apparent to those of ordinary skill in the art that variations and modifications, or appropriate alterations and combinations, of the pure zinc materials and methods of making and using the same described herein may be made to implement and use the techniques of the present invention 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, and the preparation method comprises the following steps:
1. pretreatment of pure zinc substrates
Carrying out cutting, polishing and solvent ultrasonic cleaning treatment on a pure zinc material;
2. ultrasonic degreasing
Immersing the bright and clean pure zinc material into alkaline degreasing liquid, then carrying out ultrasonic cleaning and drying;
3. preparation of 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 in a micro-arc oxidation electrolyte, wherein the pure zinc is connected with the anode of a power supply to be used as the anode, and a stainless steel electrolytic cell is connected with the cathode of the power supply to be used as the cathode; turning on the refrigerating device and controlling the temperature; adopting a micro-arc oxidation alternating current pulse power supply to start power supply, wherein the positive voltage and the negative voltage are respectively + 30V- +60V, -20-40V under a constant voltage mode, the pulse frequency is fixed at 0.1-0.3 Hz, the duty ratio is set at 70% -90%, and performing micro-arc oxidation to obtain a pure zinc material with a micro-arc oxidation coating on the surface;
5. plate post-treatment
All samples were rinsed with deionized water and dried at ambient temperature.
Unless otherwise specified, the experimental environmental and parametric conditions for each group in the test were kept consistent, except for the differences explicitly indicated.
The medical pure zinc material provided by the invention, the preparation method and the application thereof are further explained below.
Example 1: preparing the medical pure zinc material
First, preparation method
1. Pretreatment of pure zinc substrates
The pure zinc substrate is No. 0 zinc, and the element components (mass fraction) 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 25mm multiplied by 2mm by linear cutting, then carrying out coarse grinding by using 240# silicon carbide abrasive paper, removing obvious processing traces existing on the surface and the periphery of a pure zinc matrix test piece, then carrying out fine grinding by using 400# → 800# → 1000# → 2000# silicon carbide abrasive paper, wherein the fine grinding effect achieves the purposes that the surface is bright, no obvious scratches exist and the lines are consistent, then carrying out ultrasonic cleaning for 10min in acetone, absolute ethyl alcohol and deionized water respectively, and carrying out air drying by using an electric hair drier, thereby obtaining a pretreated pure zinc matrix;
2. ultrasonic degreasing
Immersing bright and clean pure zinc into deoiling liquid which is 10% sodium hydroxide solution at the temperature of 60 ℃, then carrying out ultrasonic cleaning for 10min, taking out the pure zinc, cleaning for 3 times with clear water, and drying by using an electric hair drier to obtain an ultrasonically treated pure zinc matrix;
3. preparation of micro-arc oxidation electrolyte
The formula of the micro-arc oxidation electrolyte is 25g/L, 3L of deionized water is added into an electrolytic tank in the first step, 75g of sodium phosphate is added into the electrolytic tank in the second step, and the mixture is fully stirred until the solution is completely dissolved, so that the micro-arc oxidation electrolyte is obtained. The micro-arc oxidation electrolyte needs to be replaced every time the micro-arc oxidation operation is performed, and the prepared micro-arc oxidation electrolyte needs to be used within 24 hours every time, so that the micro-arc oxidation electrolyte is prevented from deteriorating;
4. micro-arc oxidation
Placing the pure zinc subjected to surface pretreatment in a micro-arc oxidation electrolyte, wherein the pure zinc is connected with the positive electrode of a power supply to be used as the positive electrode, a stainless steel electrolytic cell is connected with the negative electrode of the power supply to be used as the negative electrode, and the distance between the positive electrode and the negative electrode is controlled to be 10 cm; starting a refrigerating device, and controlling the temperature to be 30 ℃; the method comprises the following steps of starting to supply power by adopting a micro-arc oxidation alternating current pulse power supply, wherein the voltage is respectively +50V and-30V in a constant voltage mode, the voltage boosting mode is that the voltage is started from 0V, the voltage is increased gradually every 2V, the positive and negative directions are synchronously performed, the voltage reduction is quick, 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. plate post-treatment
All samples were rinsed with deionized water and dried at ambient temperature.
The flow chart of the preparation of the pure zinc material by micro-arc oxidation in the invention is shown in figure 1.
Second, performance detection
Preparing a plurality of groups of samples according to the preparation process and the same parameters, sending one group of samples to perform SEM detection, and observing and representing the surface appearance and the thickness of the coating; one group of samples are sent to be analyzed by XRD, FTIR and XPS so as to prove that the corrosion-resistant coating is successfully prepared; a group of samples develop an electrochemical experiment and test the impedance modulus value and the corrosion current density of the corrosion-resistant coating; the results of the relevant tests are as follows;
1. as shown in fig. 2, SEM images of the coating, elemental mapping of the area scan, EDS images, metallographic cross-sections and corresponding cross-sectional line scans. As can be seen from a-b of FIG. 2, micron-sized holes are uniformly distributed on the surface of the coating, and the surface has no visible defects such as holes and cracks; as can be seen from c-f of FIG. 2, elements such as O, Zn, P, etc. are uniformly distributed on the surface of the coating; as can be seen from g to f of FIG. 2, the thickness of the coating is 10 to 20 μm, and the characteristic curves of elements such as Zn, O and the like have sudden changes, which shows that the coating and the matrix have good bonding property.
2. The XRD spectrum of the coating is shown in fig. 3. It can be seen that the strong diffraction peaks found at 31.8 °, 34.6 °, and 36.5 ° can be attributed to ZnO, which is generated during the micro-arc oxidation due to Zn generated when electrolyzing zinc and water 2+ And O 2– /OH – The reaction between them. Meanwhile, the presence of zinc oxide was also confirmed by secondary peaks corresponding to 47.1 °, 56.7 °, 63.1 °, and 68.1 °. It can be seen that the coating consists essentially of ZnO.
3. An FTIR detection of the coating is shown in fig. 4. As can be seen from FIG. 4, at 433cm -1 The right and left show strong absorption peaks, which are the stretching vibration of Zn-O, indicating the successful preparation of ZnO.
4. Figure 5 shows XPS detection of the micro arc oxidized coating. As can be seen from FIG. 5, the absorption peaks of Zn, O, C and P elements have four distinct peaks. From the XRD, FTIR and XPS results, it can be seen that the coating layer is mainly composed of ZnO.
5. Fig. 6 shows a graph comparing the corrosion current density of the coated pure zinc material with that of a pure zinc substrate. As can be seen from FIG. 6, the corrosion current density and corrosion potential of the pure zinc matrix are 21.810 + -0.042 muA/cm 2 And-1.078 ± 0.013V; the corrosion current density and the 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 resistance modulus of the coating compared to a pure zinc matrix. As can be seen from fig. 7, the coating exhibits a greater modulus of resistance in both the low and high frequency regions, is more stable, and provides a better corrosion barrier for the substrate.
7. As shown in fig. 8, which shows a graph comparing the wettability contact angle of the coating with a pure zinc matrix, (a) is a pure zinc substrate; (b) is pure zinc material with coating. 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 was about 82.4 ± 0.6 °. A lower wettability contact angle indicates better biological performance, and the coated pure zinc material of the invention can interact closely with biological fluids better than a pure zinc matrix.
Comparative example 1: preparation of pure zinc material under constant current mode
Referring to the preparation process of example 1, the micro-arc oxidation was changed to a constant current mode: + 5- +9A, -3A;
scanning electron microscopy (as shown in fig. 9) observes that an uneven and non-compact coating is formed on the surface of a substrate, a plurality of micropores are distributed on the surface of the coating, but most of the micropores are corroded, the content of P element on the surface is low, and the binding force between the coating and a pure zinc substrate is poor. Through electrochemical tests (as shown in fig. 10), the coating in the comparative example cannot improve the corrosion performance of the pure zinc matrix, or even accelerate the corrosion thereof, compared with the self-corrosion potential of the pure zinc shown in fig. 6.
Comparative example 2: preparation of pure zinc material by calcium glycerophosphate electrolyte
Referring to the preparation process of example 1, the electrolytes were adjusted to other phosphates: 0.02mol/L calcium glycerophosphate;
a scanning electron microscope (as shown in FIG. 11) observes that an uneven and non-compact coating is formed on the surface of a 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 coating prepared in this comparative example is not suitable for improving the corrosion performance of the substrate.
Comparative example 3: preparation of pure zinc material at different electrolyte temperatures
Referring to the preparation process of example 1, the electrolyte temperatures were set at 10 ℃, 50 ℃ and 80 ℃, respectively;
when the temperature of the substrate is too high or too low, the coating cannot be smoothly generated, and a large number of defects (cracks and holes) exist, so that the substrate falls off greatly during cleaning, as observed by a scanning electron microscope (as shown in fig. 12). This comparative example shows that temperature has a great influence on the formation of the coating in example 1.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and amendments can be made without departing from the principle of the present invention, and these modifications and amendments should also be considered as the protection scope of the present invention.
Claims (10)
1. A medical pure zinc material is characterized in that the surface of the 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.
2. The pure zinc material of claim 1, wherein Zn in the pure zinc material is more than or equal to 99.99%.
3. The pure zinc material of claim 1 or 2, wherein the pure zinc material is zinc No. 0.
4. The pure zinc material of claim 1, wherein the concentration of the sodium phosphate electrolyte is 20-30 g/L.
5. Use of the pure zinc material according to any one of claims 1 to 4 for the preparation of a medical implant.
6. The method for preparing pure zinc material according to claim 1, comprising:
step 1, carrying out pretreatment of polishing, oil removal and cleaning on a pure zinc material;
and 2, taking the pretreated pure zinc material as a positive electrode, and performing micro-arc oxidation in a sodium phosphate electrolyte, wherein the temperature of the sodium phosphate electrolyte is kept at 25-35 ℃.
7. The method according to claim 6, wherein the step 1 is:
polishing the pure zinc material step by step, carrying out ultrasonic cleaning by adopting acetone, absolute ethyl alcohol and water, and then removing oil and cleaning by adopting alkaline degreasing liquid.
8. The method of claim 6, wherein the micro-arc oxidation is performed in an AC constant voltage mode.
9. The method of claim 8, wherein the AC constant voltage mode has a positive voltage of +30V to +60V, a negative voltage of-20V to-40V, a fixed pulse frequency of 0.1 to 0.3Hz, and a duty ratio of 70 to 90%.
10. The manufacturing method according to claim 8, wherein in the alternating constant voltage mode, the voltage boosting is started from 0V and is increased every 2V until a preset value, and the positive and negative voltages are performed synchronously; the voltage reduction 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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| Title |
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| 张昕等: ""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"", 《表面技术》, vol. 50, no. 2, pages 39 - 47 * |
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