CN112111774B - Preparation method of antibacterial micro-arc oxidation film layer - Google Patents
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Abstract
The invention discloses a preparation method of an antibacterial micro-arc oxidation film layer, which comprises the following steps: firstly, smelting and preparing the silver-containing magnesium alloy, and then carrying out micro-arc oxidation to form an antibacterial micro-arc oxidation film layer on the surface of the silver-containing magnesium alloy. The method of the invention can endow the micro-arc oxidation film layer with excellent antibacterial performance, is simple to operate, safe and reliable, and has wide application prospect in the field of orthopedic implants.
Description
Technical Field
The invention relates to a preparation method of an antibacterial micro-arc oxidation film layer, and belongs to the technical field of surface engineering.
Background
The biological magnesium alloy as bone implant material has several advantages, such as biodegradability, good biocompatibility, high specific strength and specific rigidity, etc., and magnesium is a major element of human body, is an important component of human skeleton, and plays an important role in bone metabolism. Compared with other metal materials, the Young modulus of the magnesium alloy is closer to that of human cortical bone, and the magnesium alloy is degradable, so that the potential stress shielding effect on bone tissues after the magnesium alloy is implanted is greatly reduced, and the healing of the bone tissues is facilitated. Therefore, magnesium alloys have been receiving more and more attention in hard tissue implantation and have been a long-standing research hotspot. However, the bare magnesium alloy metal has the problem that the degradation rate is fast and cannot match the healing cycle of human bone tissue, and the formation of the ceramic protective layer on the surface of the magnesium alloy through micro-arc oxidation is one of effective means for solving the problem that the degradation rate is too fast in the initial stage of magnesium alloy implantation.
With the abuse of antibiotics and the emergence of "super-resistant bacteria", the bio-magnesium alloy material has to face another problematic issue, namely bone implant related infections. The hazard of such infections is great and how to solve this problem becomes urgent. Therefore, it is required to impart a certain antibacterial property to the surface of the magnesium alloy. At present, the method for endowing the magnesium alloy micro-arc oxidation film layer with antibacterial performance mainly comprises the following two methods: 1) the compound with antibacterial performance is added into the electrolyte, and the uniformity of the distribution of the antibacterial substance inside and outside the membrane layer is greatly influenced by the size of the antibacterial substance and the dispersibility of the antibacterial substance in the electrolyte, so that the difficulty of actual operation is high, and the membrane layer with stable antibacterial performance is not easy to obtain; 2) the antibacterial coating is arranged outside the micro-arc oxidation film layer, and the antibacterial coating is easy to fall off because the combination of the antibacterial coating and the micro-arc oxidation film layer is not firm enough, and the method can increase the complexity of the process, thereby leading to the increase of the treatment cost.
Therefore, it is highly desirable to develop a method for preparing a micro-arc oxidation film with excellent antibacterial effect.
Disclosure of Invention
The invention aims to provide a preparation method of an antibacterial micro-arc oxidation film layer.
The technical scheme adopted by the invention is as follows:
a preparation method of an antibacterial micro-arc oxidation film layer comprises the following steps: firstly, smelting and preparing the silver-containing magnesium alloy, and then carrying out micro-arc oxidation to form an antibacterial micro-arc oxidation film layer on the surface of the silver-containing magnesium alloy.
Preferably, the preparation method of the antibacterial micro-arc oxidation film layer comprises the following steps:
1) polishing, pickling and drying the pure magnesium block;
2) putting the pure magnesium block treated in the step 1) into a smelting furnace, charging protective gas, heating until the pure magnesium block is completely melted, adding metallic silver particles or/and Mg-Ag intermediate alloy, heating until the metallic silver particles or/and the Mg-Ag intermediate alloy are completely melted, standing, and removing impurities on the surface of the molten material;
3) injecting the molten material in the step 2) into a mold, and demolding to obtain the silver-containing magnesium alloy;
4) putting the silver-containing magnesium alloy into a heat treatment furnace for carrying out homogenization heat treatment;
5) preparing an electrolyte;
6) connecting the silver-containing magnesium alloy subjected to the homogenization heat treatment in the step 4) with a power supply anode, immersing the silver-containing magnesium alloy into a cathode tank filled with the electrolyte in the step 5), connecting the cathode tank with a power supply cathode, and performing micro-arc oxidation to form an antibacterial micro-arc oxidation film layer on the surface of the silver-containing magnesium alloy.
Preferably, the protective gas in the step 2) is one of argon and argon-sulfur hexafluoride mixed gas.
Preferably, the mass ratio of the argon to the sulfur hexafluoride in the argon-sulfur hexafluoride mixed gas is 99: 1.
Preferably, the smelting furnace in the step 2) is a muffle furnace.
Preferably, the mold in the step 3) is preheated to 250-300 ℃ and then the molten material is injected.
Preferably, the silver content in the silver-containing magnesium alloy in the step 3) is 0.5 wt% to 25 wt%.
Further preferably, the silver content in the silver-containing magnesium alloy in the step 3) is 2 wt% to 10 wt%.
Preferably, the homogenization heat treatment in the step 4) is carried out at 350-445 ℃, and the treatment time is 6-12 h.
Preferably, the electrolyte in step 5) is one of orthophosphate system electrolyte, metaphosphate system electrolyte and silicate system electrolyte.
Preferably, the orthophosphate system electrolyte has the following composition: 5-12 g/L of sodium tripolyphosphate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent.
Preferably, the metaphosphate system electrolyte comprises the following components: 3-10 g/L of sodium hexametaphosphate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent.
Preferably, the silicate system electrolyte comprises: 5-15 g/L of sodium silicate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent.
Preferably, the power supply in the step 6) is a pulse power supply, the voltage is 450-550V, and the current density is 30-60 mA/cm2The frequency is 800-2000 Hz.
Preferably, the treatment time of the micro-arc oxidation in the step 6) is 400-900 s.
The invention has the beneficial effects that: the method of the invention can endow the micro-arc oxidation film layer with excellent antibacterial performance, is simple to operate, safe and reliable, and has wide application prospect in the field of orthopedic implants.
Specifically, the method comprises the following steps:
1) the micro-arc oxidation film layer with antibacterial performance is prepared based on the silver-containing magnesium alloy, and in the degradation process of the implant, the film layer has antibacterial performance and better carrying performance and continuity with the antibacterial performance of the silver-containing magnesium alloy matrix;
2) the silver of the micro-arc oxidation film layer with antibacterial performance is derived from silver or magnesium-silver phase which is solid-dissolved in the magnesium alloy after the homogenization heat treatment, and along with the uniform oxidation release of the surface of the magnesium alloy, the silver element is uniformly introduced into the micro-arc oxidation film layer in the form of silver compound or silver simple substance, so that the distribution uniformity of the silver element in the micro-arc oxidation film layer can be ensured;
3) according to the invention, the silver-containing magnesium alloy is subjected to micro-arc oxidation, and the micro-arc oxidation power supply parameters, the electrolyte concentration and the silver content in the magnesium alloy are strictly controlled, so that the quality of the micro-arc oxidation film layer is ensured, and the micro-arc oxidation film layer has excellent antibacterial performance;
4) the method is suitable for various micro-arc oxidation electrolyte systems, has wide application range and is suitable for large-area popularization and application.
Drawings
FIG. 1 is an SEM image of the antimicrobial micro-arc oxide film of example 1.
Fig. 2 is an SEM image of the micro arc oxide film layer in comparative example 1.
FIG. 3 is an SEM image of the antimicrobial micro-arc oxide film of example 2.
Fig. 4 is an SEM image of the micro arc oxide film layer in comparative example 2.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of an antibacterial micro-arc oxidation film layer comprises the following steps:
1) calculating and weighing pure magnesium blocks and metal silver particles with the purity higher than 99.5 wt% according to the silver content of 6 wt%, and then polishing, pickling and drying the pure magnesium blocks;
2) putting the pure magnesium block treated in the step 1) into a smelting furnace, introducing argon, heating to 720 ℃ until the pure magnesium block is melted, preserving heat for 15min, then heating to 750 ℃, adding metal silver particles, preserving heat for 15min, reducing the temperature to 680 ℃, standing for 15min, and removing impurities on the surface of the molten material;
3) injecting the molten material in the step 2) into a steel mold coated with a release agent and preheated to 280 ℃, slowly immersing the steel mold into flowing water at 20 ℃ to quickly solidify the molten material in the mold, and demolding to obtain the silver-containing magnesium alloy (specification is 15mm multiplied by 4 mm);
4) putting the silver-containing magnesium alloy into a heat treatment furnace preheated to 420 ℃, and preserving heat for 8 hours to finish homogenization heat treatment;
5) sodium tripolyphosphate (Na)3PO4) Dispersing sodium hydroxide (NaOH) and glycerol in ultrapure deionized water to prepare electrolyte with 6g/L of sodium tripolyphosphate, 6g/L of sodium hydroxide and 8mL/L of glycerol;
6) connecting the silver-containing magnesium alloy subjected to the homogenization heat treatment in the step 4) with a positive electrode of a pulse power supply, immersing the magnesium alloy into a cathode tank filled with the electrolyte in the step 5), connecting the cathode tank with a cathode of the pulse power supply, and controlling the voltage to be 550V, the frequency to be 1000Hz, and the current density to be 40mA/cm2And the stirring speed of the electrolyte is 200rpm, and the antibacterial micro-arc oxidation film layer is formed on the surface of the magnesium alloy containing silver after treatment for 400s (an SEM image is shown in figure 1).
Comparative example 1:
a preparation method of a micro-arc oxidation film layer comprises the following steps:
1) sodium tripolyphosphate (Na)3PO4) Dispersing sodium hydroxide (NaOH) and glycerol in ultrapure deionized water to prepare electrolyte with 6g/L of sodium tripolyphosphate, 6g/L of sodium hydroxide and 8mL/L of glycerol;
2) connecting a pure magnesium block (specification is 15mm multiplied by 4mm) with a positive electrode of a pulse power supply, immersing the pure magnesium block into a cathode tank filled with the electrolyte obtained in the step 1), connecting the cathode tank with a cathode of the pulse power supply, controlling the voltage to be 480V and the current density to be 40mA/cm2The frequency is 1000Hz, the stirring speed of the electrolyte is 200rpm, the micro-arc oxidation film layer is formed on the surface of the pure magnesium sheet after treatment for 600s (the SEM image is shown in figure 2).
Example 2:
a preparation method of an antibacterial micro-arc oxidation film layer comprises the following steps:
1) calculating and weighing pure magnesium blocks and metal silver particles with the purity higher than 99.5 wt% according to the silver content of 6 wt%, and then polishing, pickling and drying the pure magnesium blocks;
2) putting the pure magnesium block treated in the step 1) into a smelting furnace, introducing argon, heating to 720 ℃ until the pure magnesium block is melted, preserving heat for 15min, then heating to 750 ℃, adding metal silver particles, preserving heat for 15min, reducing the temperature to 680 ℃, standing for 15min, and removing impurities on the surface of the molten material;
3) injecting the molten material in the step 2) into a steel mold coated with a release agent and preheated to 300 ℃, slowly immersing the steel mold into flowing water at 20 ℃ to quickly solidify the molten material in the mold, and demolding to obtain the silver-containing magnesium alloy (specification is 15mm multiplied by 4 mm);
4) putting the silver-containing magnesium alloy into a heat treatment furnace preheated to 440 ℃, and preserving heat for 10 hours to finish homogenization heat treatment;
5) sodium hexametaphosphate ((NaPO)3)6) Dispersing sodium hydroxide (NaOH) and glycerol in ultrapure deionized water to prepare electrolyte with the concentration of 8g/L sodium hexametaphosphate, 6g/L sodium hydroxide and 5mL/L glycerol;
6) connecting the silver-containing magnesium alloy subjected to the homogenization heat treatment in the step 4) with a positive electrode of a pulse power supply, immersing the magnesium alloy into a cathode tank filled with the electrolyte in the step 5), connecting the cathode tank with a cathode of the pulse power supply, controlling the voltage to be 500V and the current density to be 40mA/cm2Treating the mixture for 650s at a frequency of 1000Hz and an electrolyte stirring speed of 300rpm to form an antibacterial micro-arc oxide film on the surface of the magnesium alloy containing silver (shown in an SEM image in figure 3).
Comparative example 2:
a preparation method of a micro-arc oxidation film layer comprises the following steps:
1) sodium hexametaphosphate ((NaPO)3)6) Dispersing sodium hydroxide (NaOH) and glycerol in ultrapure deionized water to prepare electrolyte with the concentration of 8g/L sodium hexametaphosphate, 6g/L sodium hydroxide and 5mL/L glycerol;
2) connecting a pure magnesium block (specification is 15mm multiplied by 4mm) with a positive electrode of a pulse power supply, immersing the pure magnesium block into a cathode tank filled with the electrolyte obtained in the step 1), connecting the cathode tank with a cathode of the pulse power supply, and controlling the voltage to be 490V and the current density to be 40mA/cm2The frequency is 1000Hz, the stirring speed of the electrolyte is 250rpm, the micro-arc oxidation film layer is formed on the surface of the pure magnesium sheet after treatment for 800s (the SEM image is shown in figure 4).
And (3) performance testing:
1) with reference to "GB/T16886.12-2005 medical device biological evaluation", degradation rates of the pure magnesium block, the micro-arc oxidation film layer of comparative example 1, the micro-arc oxidation film layer of comparative example 2, the silver-containing magnesium alloy of example 1, the antibacterial micro-arc oxidation film layer of example 1, and the antibacterial micro-arc oxidation film layer of example 2 after soaking for one week under simulated physiological conditions were tested, and the test results are shown in the following table:
TABLE 1 degradation Rate test results
| Material | Degradation Rate (mm/a) |
| Pure magnesium block (purity)>99.5wt％) | 0.36 |
| Micro-arc oxidation film layer of comparative example 1 | 0.05 |
| Comparative example 2 micro-arc oxide film layer | 0.08 |
| Silver-containing magnesium alloy of example 1 | 1.52 |
| EXAMPLE 1 antimicrobial micro-arc Oxidation film layer | 0.10 |
| EXAMPLE 2 antimicrobial micro-arc oxide film layer | 0.09 |
Note:
the degradation rate (MDR) calculation formula is as follows:
As can be seen from Table 1: the degradation rate of the pure magnesium block and the silver-containing magnesium alloy is greatly reduced after micro-arc oxidation treatment.
2) The direct contact method is used for testing the sterilization rate of pure magnesium blocks, the micro-arc oxidation film layer of the comparative example 1, the micro-arc oxidation film layer of the comparative example 2, the silver-containing magnesium alloy of the example 1, the antibacterial micro-arc oxidation film layer of the example 1 and the antibacterial micro-arc oxidation film layer of the example 2 on escherichia coli, and the test results are shown in the following table:
TABLE 2 results of the bactericidal ratio test
| Material | Antibacterial Properties (colony method) |
| Pure magnesium block (purity)>99.5wt％) | 62.0％ |
| Micro-arc oxidation film layer of comparative example 1 | 12.3％ |
| Comparative example 2 micro-arc oxide film layer | 10.9％ |
| Silver-containing magnesium alloy of example 1 | >99.9％ |
| EXAMPLE 1 antimicrobial micro-arc Oxidation film layer | 95.4％ |
| EXAMPLE 2 antimicrobial micro-arc oxide film layer | 92.7％ |
As can be seen from Table 2: the micro-arc oxidation film layer formed on the silver-containing magnesium alloy has excellent antibacterial and bactericidal effects.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (4)
1. A preparation method of an antibacterial micro-arc oxidation film layer is characterized by comprising the following steps: the method comprises the following steps: firstly, smelting and preparing the silver-containing magnesium alloy, and then carrying out micro-arc oxidation to form an antibacterial micro-arc oxidation film layer on the surface of the silver-containing magnesium alloy;
the method specifically comprises the following steps:
1) polishing, pickling and drying the pure magnesium block;
2) putting the pure magnesium block treated in the step 1) into a smelting furnace, charging protective gas, heating until the pure magnesium block is completely melted, adding metallic silver particles or/and Mg-Ag intermediate alloy, heating until the metallic silver particles or/and the Mg-Ag intermediate alloy are completely melted, standing, and removing impurities on the surface of the molten material;
3) injecting the molten material in the step 2) into a mold, and demolding to obtain the silver-containing magnesium alloy;
4) putting the silver-containing magnesium alloy into a heat treatment furnace for carrying out homogenization heat treatment;
5) preparing an electrolyte;
6) connecting the silver-containing magnesium alloy subjected to the homogenization heat treatment in the step 4) with a power supply anode, immersing the silver-containing magnesium alloy into a cathode tank filled with the electrolyte in the step 5), connecting the cathode tank with a power supply cathode, and performing micro-arc oxidation to form an antibacterial micro-arc oxidation film layer on the surface of the silver-containing magnesium alloy;
step 3) the silver content in the silver-containing magnesium alloy is 0.5 wt% -25 wt%;
step 5) the electrolyte is one of orthophosphate system electrolyte, metaphosphate system electrolyte and silicate system electrolyte;
the orthophosphate system electrolyte comprises the following components: 5-12 g/L of sodium tripolyphosphate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent;
the metaphosphate system electrolyte comprises the following components: 3-10 g/L of sodium hexametaphosphate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent;
the silicate system electrolyte comprises the following components: 5-15 g/L of sodium silicate, 2-8 g/L of sodium hydroxide, 4-10 mL/L of glycerol and water as a solvent;
the power supply in the step 6) is a pulse power supply, the voltage is 450-550V, and the current density is 30-60 mA/cm2The frequency is 800-2000 Hz;
and 6) the treatment time of the micro-arc oxidation is 400-900 s.
2. The method for preparing the antibacterial micro-arc oxidation film layer according to claim 1, characterized in that: and 2) the protective gas is one of argon and argon-sulfur hexafluoride mixed gas.
3. The method for preparing the antibacterial micro-arc oxidation film layer according to claim 1, characterized in that: and 3) preheating the die to 250-300 ℃, and then injecting molten materials.
4. The method for preparing the antibacterial micro-arc oxidation film layer according to any one of claims 1 to 3, characterized in that: and 4) carrying out homogenization heat treatment at 350-445 ℃, wherein the treatment time is 6-12 h.
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