CN111588904B - Iodine-loaded titanium alloy medical component containing polycaprolactone/povidone iodine surface layer and manufacturing method thereof - Google Patents
Iodine-loaded titanium alloy medical component containing polycaprolactone/povidone iodine surface layer and manufacturing method thereof Download PDFInfo
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- CN111588904B CN111588904B CN202010565317.5A CN202010565317A CN111588904B CN 111588904 B CN111588904 B CN 111588904B CN 202010565317 A CN202010565317 A CN 202010565317A CN 111588904 B CN111588904 B CN 111588904B
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 48
- 229920001610 polycaprolactone Polymers 0.000 title claims abstract description 43
- 239000004632 polycaprolactone Substances 0.000 title claims abstract description 43
- CPKVUHPKYQGHMW-UHFFFAOYSA-N 1-ethenylpyrrolidin-2-one;molecular iodine Chemical compound II.C=CN1CCCC1=O CPKVUHPKYQGHMW-UHFFFAOYSA-N 0.000 title claims abstract description 37
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011630 iodine Substances 0.000 title claims abstract description 35
- 229910052740 iodine Inorganic materials 0.000 title claims abstract description 35
- 229920000153 Povidone-iodine Polymers 0.000 title claims abstract description 24
- 229960001621 povidone-iodine Drugs 0.000 title claims abstract description 24
- 239000002344 surface layer Substances 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 38
- 238000007745 plasma electrolytic oxidation reaction Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000007943 implant Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 18
- 239000010410 layer Substances 0.000 claims description 16
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 11
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- 238000012986 modification Methods 0.000 claims description 10
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- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims description 3
- UHHRFSOMMCWGSO-UHFFFAOYSA-L calcium glycerophosphate Chemical compound [Ca+2].OCC(CO)OP([O-])([O-])=O UHHRFSOMMCWGSO-UHFFFAOYSA-L 0.000 claims description 3
- 229940095618 calcium glycerophosphate Drugs 0.000 claims description 3
- 235000019299 calcium glycerylphosphate Nutrition 0.000 claims description 3
- 239000001506 calcium phosphate Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 235000019691 monocalcium phosphate Nutrition 0.000 claims description 3
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 3
- 230000000399 orthopedic effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
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- 238000002848 electrochemical method Methods 0.000 claims description 2
- 238000003487 electrochemical reaction Methods 0.000 claims description 2
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- 238000000576 coating method Methods 0.000 abstract description 7
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
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- 239000002253 acid Substances 0.000 description 5
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 241000191967 Staphylococcus aureus Species 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
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- 238000004140 cleaning Methods 0.000 description 3
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- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
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- 229920001577 copolymer Polymers 0.000 description 2
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- 239000003480 eluent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
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- 229910052751 metal Inorganic materials 0.000 description 2
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- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000002188 osteogenic effect Effects 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- FAAHNQAYWKTLFD-UHFFFAOYSA-N 1-butan-2-ylpyrrolidin-2-one Chemical compound CCC(C)N1CCCC1=O FAAHNQAYWKTLFD-UHFFFAOYSA-N 0.000 description 1
- 206010064687 Device related infection Diseases 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 206010042566 Superinfection Diseases 0.000 description 1
- 239000011543 agarose gel Substances 0.000 description 1
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- 238000000861 blow drying Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000021164 cell adhesion Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
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- 238000007654 immersion Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
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- 238000005488 sandblasting Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
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- 230000003746 surface roughness Effects 0.000 description 1
- 238000001356 surgical procedure Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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Abstract
The invention provides an antibacterial iodine-carrying titanium alloy medical component containing a polycaprolactone/povidone iodine surface layer and a manufacturing method thereof, wherein an iodine-containing coating is fixed on a titanium alloy by a micro-arc oxidation reaction and surface iodine modification method, and a high polymer composite structure is constructed on the structure, so that stable antibacterial performance is obtained; the material prepared by the process has obvious broad-spectrum antibacterial action, and the antibacterial active ingredient is iodine; in addition, the defects that the iodine on the surface of the material is unstable and volatile are overcome by constructing the surface layer structure of polycaprolactone/povidone iodine, and the stability of the antibacterial performance of the material is guaranteed; and along with the gradual degradation of the surface layer structure, the iodine below the surface layer structure is gradually released, so that the effective antibacterial duration of the material is prolonged to a certain extent; the invention can effectively reduce the early infection and the related complications which appear after the surgical operation using the titanium alloy implant.
Description
Technical Field
The invention relates to an iodine-carrying titanium alloy medical component containing a polycaprolactone/povidone iodine surface layer and a manufacturing method thereof.
Background
With the development of medical material technology, the application range and the use amount of the medical internal implant are gradually increased year by year in the global range. Therefore, the related infection caused by the internal implant also becomes a problem which is difficult to avoid and troublesome for the present clinician. At this stage, the treatment of such infections is mainly done clinically by systemic application of antibiotics. However, this treatment requires the application of sufficient amounts of antibiotics for a long period of time, which can cause the normal flora of the human body to become dysregulated, presenting a superinfection, and in severe cases being life threatening. In addition, in the case of internal implant-related infection, local blood supply at the infection focus is generally poor and bacteria often form a biofilm inhibiting drug permeation, resulting in low blood concentration at and near the infection focus and difficulty in exerting antibiotic effect. Therefore, the modification treatment of the surface of the internal implant to make the surface have the anti-infection property is an effective method for solving the related infection of the internal implant.
The micro-arc oxidation method is a novel surface modification method. The metal surface coating formed by micro-arc oxidation is an extremely thin oxidation insulation layer immediately generated on the metal surface after electrification. The electrolytic ions of the reaction solution can participate in the physical and chemical reaction of the micro-arc reaction discharge area, break down the oxide film and deposit in the coating. Therefore, researchers have utilized this phenomenon to introduce calcium and phosphorus elements into the coating, and have achieved the goal of improving the bioactivity of the coating. The literature proves that the titanium dioxide coating prepared on the titanium substrate by utilizing the micro-arc oxidation technology not only has the characteristic of inducing the growth of hydroxyapatite on the surface of the material, but also has good cell adhesion characteristic. The invention also applies the solution containing calcium and phosphorus to carry out micro-arc oxidation, and the surface area of the material is increased to increase the iodine adhesion area, and simultaneously the base material has certain biological activity.
Polycaprolactone is a high polymer with good biological safety and biodegradability, and the degradation product is CO2And H2And O. The literature reports that after the molecular fragments of polycaprolactone degraded in vivo are phagocytized by phagocytes, the degraded products in cells can be excreted out of the body by random normal metabolism. At present, polycaprolactone is widely applied to the fields of medicine and biology, such as the construction of controllable drug release carriers, cell and tissue culture pedestals, the manufacture of completely degradable plastic surgical sutures, medical modeling materials and the like.
Iodine and iodine compounds have strong antibacterial performance. At present, a plurality of iodine and compounds thereof are used in the medical disinfection field including skin and partial mucosa, and have good biological safety. The method of modifying iodine and its compound on the surface of material can endow the material with reliable bacteriostasis performance.
According to the invention, the copolymer surface layer of Polycaprolactone (PCL)/povidone iodine (PVP-I) is constructed on the iodine-carrying titanium alloy part, so that the original high biological safety of PCL is maintained, the material is endowed with early antibacterial performance, and the problem that iodine generated by simply carrying iodine on the surface of the titanium alloy is difficult to stably and continuously exist is solved. In addition, when the PCL/PVP-I copolymerization layer on the surface layer is continuously degraded, the iodine of the iodine modification layer below the PCL/PVP-I copolymerization layer is slowly released, and the effect of prolonging the bacteriostatic effective time is further achieved. Meanwhile, the material surface can also show certain osteogenic activity along with the gradual increase of the exposure proportion of the micro-arc oxidation layer.
Disclosure of Invention
The invention aims to provide an iodine-carrying titanium alloy medical component with a polycaprolactone/povidone iodine surface layer and antibacterial property and a manufacturing method thereof, aiming at the problem of implant infection caused by the use of a titanium alloy medical material in the field of orthopedic surgery.
The invention uses PCL/PVP-I and potassium iodide solution to carry out modification treatment on the surface of the micro-arc titanium oxide alloy, and mainly comprises three steps of constructing a porous iodine-carrying layer, modifying the iodine surface and constructing a polycaprolactone/povidone iodine surface layer on the surface.
The technical scheme of the invention is as follows:
an iodine-carrying titanium alloy medical component comprises a titanium alloy base material, a porous iodine modification layer and a polycaprolactone/povidone iodine surface layer from inside to outside in sequence;
the preparation method of the iodine-carrying titanium alloy medical component comprises the following steps:
(1) immersing the titanium alloy base material subjected to surface pretreatment into an electrolytic bath solution for electrochemical treatment to form a surface porous film structure;
specifically, the surface pretreatment method comprises the following steps: polishing, sand blasting and impurity removing are carried out on the material, and the impurity removing comprises the following steps: washing with acetone (more than or equal to 99.5%), ethylene glycol (more than or equal to 99.5%) and ultrapure water in sequence, then acid washing, and finally ultrasonic cleaning; the acid cleaning adopts HF and HNO3、H3PO4The acid washing time of the mixed acid solution is 5-25 min; the ultrasonic cleaning comprises the following steps: cleaning the material in ultrapure water for 5 min/time, and circulating for 3 times;
the electrochemical treatment is anodic oxidation or micro-arc oxidation; the electrolytic cell solution comprises: 1-20g/L of calcium acetate, 1-20g/L of monocalcium phosphate, 10-20g/L of ethylene diamine tetraacetic acid disodium salt, 1-20g/L of calcium glycerophosphate and deionized water as a solvent; in the electrochemical reaction process, the titanium alloy base material is placed on a titanium alloy hook or a mesh basket to be used as an anode, a pure titanium plate is used as a cathode, the distance between the anode and the cathode is 10-30cm, the voltage is controlled to be 200-700V in the reaction period, the frequency is controlled to be 100-500HZ, the duty ratio is 10-30%, the temperature is controlled to be 20-40 ℃, and the reaction time is 2-15 min;
the thickness of the obtained porous film is 5-20 μm;
(2) performing surface iodine modification on the titanium alloy material with the porous film structure on the surface obtained in the step (1) by using an electrochemical method, wherein the operation conditions are as follows: taking a potassium iodide aqueous solution as an electrolyte, placing the material on a titanium alloy hook or a mesh basket as an anode under the conditions of normal temperature (20-30 ℃) and constant pressure of 15-60V in a dark place, taking a pure titanium plate as a cathode, wherein the distance between the anode and the cathode is 10-20cm, and the reaction time is 10-70 min;
the concentration of the potassium iodide aqueous solution is 0.01-0.05 mol/L;
(3) immersing the titanium alloy material modified by the iodine in the step (2) into the polycaprolactone/povidone iodine dip coating solution, reacting for 5-20s, and volatilizing to obtain the iodine-carrying titanium alloy medical component containing the polycaprolactone/povidone iodine surface layer;
the operation of immersing the material in the dip-coating solution for reaction can be repeated for 2-3 times;
in the polycaprolactone/povidone iodine dip-coating solution, the concentration of polycaprolactone (with molecular weight of 5-8 ten thousand) is 0.5-15g/dL, the concentration of povidone iodine is 0.5-2g/dL, and the solvent is dichloromethane;
the operation method of the volatilizing comprises the following steps: and placing the material after dip coating in a vacuum exhaust device for 10-18h to exhaust residual dichloromethane.
The iodine content of the surface of the prepared polycaprolactone/povidone iodine-containing surface iodine-loaded titanium alloy medical component containing the surface layer is 0.5-2 wt%, and the application of the product of the invention includes but is not limited to the range of internal and external fixation and implants of orthopedics. The titanium alloy medical component has obvious bacteriostatic action on common infectious strains of surgical operations, such as staphylococcus aureus, escherichia coli and the like, the effective bacteriostatic components of the titanium alloy medical component are iodine and iodine compounds, including iodine simple substance and povidone iodine, and polycaprolactone with good biological safety and biodegradability is introduced to the surface of the titanium alloy to form a copolymer with the povidone iodine.
The invention has the advantages that:
the invention utilizes iodine with good biological safety and iodine compounds with strong antibacterial performance, and constructs the polycaprolactone/povidone iodine copolymer surface layer on the iodine-carrying titanium alloy component, thereby not only retaining the original high biological safety of polycaprolactone, but also endowing the material with early antibacterial performance, and simultaneously solving the problem that iodine which is only carried on the surface of the titanium alloy is difficult to stably and continuously exist.
In addition, when the PCL/PVP-I copolymerization layer on the surface layer is continuously degraded, the iodine of the iodine modification layer below the PCL/PVP-I copolymerization layer is slowly released, and the effect of prolonging the bacteriostatic effective time is further achieved. Meanwhile, the material surface can also present certain osteogenic activity along with the gradual increase of the exposure proportion of the micro-arc oxidation layer.
The preparation method has the advantages of simple preparation process, proper reaction conditions, high efficiency, low cost and good repeatability, and the obtained titanium alloy medical component has a very obvious antibacterial effect.
Drawings
FIG. 1: the material prepared by the invention has a schematic main structure, wherein a is a PCL/PVP-I structure layer, b is an iodine modification area, c is a porous micro-arc oxidation layer, and d is a titanium alloy layer.
FIG. 2: EDS analysis results of the surface of the iodine-carrying titanium alloy material containing the polycaprolactone/povidone iodine surface layer.
FIG. 3: and (3) performing micro-arc oxidation and PCL/PVP-I dip-coating drying on the surface of the material, wherein the magnification is 5000 times, a is an electron microscope observation image of the surface structure of the micro-arc oxidation layer, and b is a PCL/PVP-I copolymerization surface layer electron microscope observation image.
FIG. 4: the detection result of the eluent after the bacteria culture on the surface of the material is as follows: a is a comparison group made of common titanium alloy material; b is an experimental group, namely an iodine-carrying titanium alloy material containing a polycaprolactone/povidone iodine surface layer.
FIG. 5: after the three materials are placed in a light environment for 1 day and 3 days, the surface bacteriostasis effect detection is carried out: the reference group is a common titanium alloy sample sheet; group A is sample wafer for direct anodic oxidation iodine-carrying treatment; group B is the PCL/PVP-I surface layer modified sample prepared according to example 1.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the invention is not limited thereto.
Example 1
1. The material (supplied by Zhejiang Uhui medical instruments Co., Ltd.) was polished and sandblasted to have a surface roughness Ra value in the range of 0-0.4. mu.m. Pretreating with acetone (not less than 99.5%), ethylene glycol (not less than 99.5%), ultrapure water, etc., and adding HF (not less than 40%, 20ml/L) and HNO3(65.0～68.0％，80ml/L)、H3PO4Acid washing in solution system (85%, 15ml/L) for 15min, finally ultrasonic cleaning for 3 times, and blow drying.
2. And (3) carrying out micro-arc oxidation on the material subjected to the step (1), wherein the reaction solution system is as follows: calcium acetate (AR,10g/L), monocalcium phosphate (AR,10g/L), ethylenediaminetetraacetic acid disodium salt (AR, 15g/L), calcium glycerophosphate (AR,10g/L), the material being immobilized on the anode side, the distance between the anode side and the cathode side being 25cm, the reaction conditions being: the voltage is 300V, the frequency is 100HZ, the duty ratio is 10 percent, the water temperature is 30 ℃, and the reaction time is 2 min; and finally, placing the sample subjected to the oxidation operation in an aqueous solution for ultrasonic immersion cleaning for 3min, and circulating for 3 times.
3. And (3) placing the material subjected to the step (2) in an aqueous solution containing 0.03mol/L potassium iodide, and carrying out iodine impregnation treatment under the constant pressure of 30V in a dark condition, wherein the material is fixed on the anode side, the distance between the anode and the cathode is 20cm, and the reaction time is 45 min. Finally, washing with purified water for 3 times to remove impurities.
4. Weighing polycaprolactone (CAS number: 24980-41-4, molecular weight 8 ten thousand, Shanghai jin Hui biological science and technology Co., Ltd.), dissolving in dichloromethane solution, stirring for 20-30min to dissolve polycaprolactone completely, and preparing into a solution system with concentration of 5 g/dL; then PVP-I powder (Ron reagent CAS number: 25655-41-8) is slowly added into the polycaprolactone solution which is completely dissolved for a plurality of times, and the mixture is fully stirred until the solution is completely dissolved, so that the PVP-I content in the solution is 1.0 g/dL. And (3) immersing the material subjected to the step (3) in the dip-coating liquid for 5-20s, uniformly lifting, repeating the operation for 3 times, then placing in a vacuum exhaust device for 18h, and performing irradiation sterilization for later use.
5. Bacteriostatic experiments of the iodine-carrying titanium alloy implant: the antibacterial detection method adopts staphylococcus aureus (ATCC 25923) as experimental bacteria, selects a common titanium sheet with the side length of 10mm and the height of 2mm and an iodine-carrying titanium sheet containing a polycaprolactone/povidone iodine surface layer, sterilizes two groups of titanium sheets and places the titanium sheets in a 24-hole plate, and each group is provided with 3 compound holes. Staphylococcus aureus (ATCC 25923) bacterial liquid (about 2-5X 10)6CFU/ml) was inoculated in a volume of 100. mu.l per well to each of the above groups of titanium plates, and the plates were subjected to static culture at 37 ℃ for 18 hours in a constant humidity environment. Bacteria adhered to the surface of the titanium sheet are eluted by sterile PBS, the eluent is diluted to a proper concentration in an equal proportion, and then an agarose gel culture dish is coated, and the bacteria colony is counted and photographed after being cultured for 24 hours at 37 ℃ in an incubator (the result is shown in figure 4).
6. And (3) coating bacteriostatic stability test: dividing the titanium alloy sample into a control group, an A group and a B group; wherein the control group sample is not subjected to operations except impurity removal and disinfection; the group A samples are prepared into iodine-carrying titanium alloy sample wafers according to the prior art (the preparation process refers to Chinese patent document CN 102416202A); and preparing the group B samples according to the steps 1-4 to obtain the PCL/PVP-I surface layer modified iodine-carrying sample. Placing the samples of the control group, the group A and the group B in natural light at room temperature at 20-30 deg.C for 24h and 72h, and performing antibacterial detection on the obtained sample according to step 5 to obtain the results shown in FIG. 5. The results suggest that compared with the prior art, the material prepared by the invention has obvious advantages in the aspects of bacteriostasis effect and maintenance of the stability of the effective bacteriostasis component iodine.
Claims (4)
1. The iodine-carrying titanium alloy medical component is characterized in that a titanium alloy base material, a porous iodine modification layer and a polycaprolactone/povidone iodine surface layer are sequentially arranged from inside to outside;
the preparation method of the iodine-carrying titanium alloy medical component comprises the following steps:
(1) immersing the titanium alloy base material subjected to surface pretreatment into an electrolytic bath solution for electrochemical treatment to form a surface porous film structure; the electrochemical treatment is anodic oxidation or micro-arc oxidation; the electrolytic cell solution comprises: 1-20g/L of calcium acetate, 1-20g/L of monocalcium phosphate, 10-20g/L of ethylene diamine tetraacetic acid disodium salt, 1-20g/L of calcium glycerophosphate and deionized water as a solvent; in the electrochemical reaction process, the titanium alloy base material is placed on a titanium alloy hook or a mesh basket to be used as an anode, a pure titanium plate is used as a cathode, the distance between the anode and the cathode is 10-30cm, the voltage is controlled to be 200-700V in the reaction period, the frequency is controlled to be 100-500HZ, the duty ratio is 10-30%, the temperature is controlled to be 20-40 ℃, and the reaction time is 2-15 min;
(2) performing surface iodine modification on the titanium alloy material with the porous film structure on the surface obtained in the step (1) by using an electrochemical method;
(3) and (3) immersing the titanium alloy material modified by the iodine in the step (2) into the polycaprolactone/povidone iodine dip-coating solution, reacting for 5-20s, and volatilizing to obtain the iodine-carrying titanium alloy medical component containing the polycaprolactone/povidone iodine surface layer.
2. The iodine-carrying titanium alloy medical member as set forth in claim 1, wherein in the step (2) of the production method, the operating conditions for the surface iodine modification are as follows: taking potassium iodide aqueous solution as electrolyte, placing the material on a titanium alloy hook or a mesh basket as an anode under the conditions of normal temperature and constant pressure of 15-60V in the dark, taking a pure titanium plate as a cathode, and reacting for 10-70min, wherein the distance between the anode and the cathode is 10-20 cm; the concentration of the potassium iodide aqueous solution is 0.01-0.05 mol/L.
3. The iodine-carrying titanium alloy medical member as set forth in claim 1, wherein in said step (3) of the production method, the operation of immersing the material in the dip-coating solution for reaction is repeated 2 to 3 times; in the polycaprolactone/povidone iodine dip-coating liquid, the concentration of polycaprolactone is 0.5-15g/dL, the concentration of povidone iodine is 0.5-2g/dL, and the solvent is dichloromethane.
4. The use of the iodine-bearing titanium alloy medical component of claim 1 as an orthopedic internal-external fixation and implant.
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