CN111705347B - Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application - Google Patents

Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application Download PDF

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CN111705347B
CN111705347B CN202010508079.4A CN202010508079A CN111705347B CN 111705347 B CN111705347 B CN 111705347B CN 202010508079 A CN202010508079 A CN 202010508079A CN 111705347 B CN111705347 B CN 111705347B
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sheet
iodine
egda
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宋青
李鹏
黄维
霍静静
高玲玲
刘新月
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Northwestern Polytechnical University
Ningbo Research Institute of Northwestern Polytechnical University
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Ningbo Research Institute of Northwestern Polytechnical University
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Abstract

The invention discloses a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method and application, and belongs to the technical field of materials. In order to overcome the defect that iodine is not easy to fix on the surface of a medical titanium implant, the invention provides a simple and efficient preparation method of an iodine coating. Preparing a Titanium Nano Tube (TNT) with controllable tube diameter and tube length on the surface of a titanium material by a constant-pressure direct-current anodic oxidation method, then copolymerizing and depositing 1-vinyl-2-pyrrolidone (VP) and cross-linked molecular Ethylene Glycol Diacrylate (EGDA) on the surface of the TNT by a high-molecular chemical vapor deposition method under a mild reaction condition to form TNT-P (VP-co-EGDA), then complexing with iodine (I) under the mild condition to prepare TNT-P (VP-co-EGDA) -I, and fixing I on the surface of the TNT, so that the titanium material has a function of killing microorganisms and has an obvious effect on drug-resistant bacteria. The insolubility of P (VP-co-EGDA) on the surface of TNT is beneficial to fixing I on the surface of a medical titanium instrument, so that the infection caused by bacteria on the surface is reduced, and the drug resistance is not generated.

Description

Method for preparing titanium nanotube iodine coating by chemical vapor deposition method and application
Technical Field
The invention belongs to the technical field of materials, relates to preparation of a titanium nanotube iodine coating, and particularly relates to a method for preparing poly (1-vinyl-2-pyrrolidone) film fixed iodine on the surface of a titanium nanotube by a chemical vapor deposition method and application thereof.
Background
Statistically, an average of 2% to 5% of implant surgery failures are due to biomaterial-related infections. Biomedical titanium (Ti) materials have been widely used in hard tissue implantation surgery due to their excellent mechanical properties and good corrosion resistance. However, since Ti material itself has no antibacterial property, it is very vulnerable to bacterial infection to form a biofilm on its surface, which may cause infection.
A large number of researches show that the anodic oxidation technology can construct a titanium nanotube array (TNT) which is ordered in height, is not limited by shape and is easy to control the tube diameter and the tube length on the surface of a titanium material, the tubular structure is favorable for conveying oxygen and nutrient substances, can promote the generation of vascular tissues and improve the bioactivity of the titanium material, and in addition, the tubular sequence can be used as a drug reservoir to load functional molecules. By loading the TNT tube with antibiotics, infections can be prevented and treated. However, abuse of antibiotics has caused a crisis of resistance worldwide. Therefore, the TNT tube is loaded with the antibacterial agent without drug resistance risk, which is beneficial to reducing the risk of postoperative drug-resistant bacterial infection and improving the success rate of the implant operation.
Povidone-iodine (also known as iodophor) is an amorphous combination of iodine (I) and poly-1-vinyl-2-pyrrolidone (PVP) and is used therapeutically as a broad spectrum antiseptic. However, the antibacterial agent has good water solubility, and cannot form a stable coating when being directly coated on the surface of the titanium material. Ethylene Glycol Diacrylate (EGDA) is a cross-linking agent with good biocompatibility, PVP can be fixed on the surface of TNT through a cross-linking reaction with 1-vinyl-2-pyrrolidone (VP), and iodine is stably combined by utilizing the complexing effect of the PVP and the iodine.
The chemical vapor deposition technology of the polymer can effectively coat a stable PVP polymer coating on the surface of the TNT, and the reaction process does not use an organic solvent and has controllable film thickness. The thickness of the coating is difficult to control by the traditional liquid-phase polymer coating preparation method (such as spraying, dip coating, spin coating and the like), and a uniform coating is difficult to form on the surface with a complex structure; moreover, organic solvents are often used in the coating preparation process, and therefore, the coating is not suitable for substrates sensitive to organic solvents, and meanwhile, the residue of the organic solvents can cause harm to human health. Therefore, P (VP-co-EGDA) is stably deposited on the TNT pipe wall by a green high-molecular chemical vapor deposition method, and is further complexed with I, so that a stable coating capable of continuously releasing iodine is constructed, the surface of the Ti implant is successfully subjected to antibiosis, and the Ti implant has a good clinical application prospect in terms of improvement of post-operation infection of the Ti-based implant and resistance to drug-resistant bacteria infection.
Disclosure of Invention
In order to stably fix PVP-I on the surface of a Ti-based material, the invention provides a method for preparing an iodine fixing polymer coating on the surface of a Ti nanotube by a chemical vapor deposition method and application thereof. By a high molecular chemical vapor deposition method, VP is stably fixed on the surface of a Ti material (TNT) with nanotubes on the surface through a cross-linking agent EGDA to form a P (VP-co-EGDA) film, and then the film is complexed with I under a mild condition to form a TNT-P (VP-co-EGDA) -I (VP: N-vinyl-2-pyrrolidone, 1-vinyl-2-pyrrolidone; EGDA: ethylene glycol diacrylate, ethylene glycol diacrylate; I: iodine) coating. The P (VP-co-EGDA) -I coating plated on the surface of the TNT kills pathogenic microorganisms through the release of I, so that the modified Ti material has a high-efficiency anti-infection function.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method comprises the following steps:
forming a Ti nanotube array on the surface of a Ti sheet by adopting a constant-voltage direct-current anodic oxidation method, and then calcining and ultrasonically treating to obtain a TNT sheet with nanotubes on the surface;
the TNT sheet with the nanotube on the surface is placed on a sample table of a reactor for chemical vapor deposition, and then an initiator di-tert-butyl peroxide, 1-vinyl-2-pyrrolidone and a cross-linking agent ethylene glycol diacrylate are respectively heated to be gasified and flow into the reactor;
arranging a nickel-chromium wire above the reaction table and heating to a desired temperature; the initiator enters a reactor, is heated and decomposed by a nickel-chromium wire to generate free radicals, further initiates the free radical chain type polymerization reaction of the 1-vinyl-2-pyrrolidone and the cross-linking agent, and the synthesized high polymer is deposited on a substrate material to form a film; when the film thickness reaches the expected requirement, the inflow of the 1-vinyl-2-pyrrolidone and the cross-linking agent is stopped; after the reaction is finished, washing the sample with water to remove residual monomers, and airing to obtain the TNT sheet with the surface modified with the polymer film;
immersing the TNT sheet of the surface modified polymer film in the solution I2And putting the TNT/NaI solution on a shaking bed to perform a complex reaction of the polymer film and iodine, then taking out and washing to remove free iodine on the surface, and airing to obtain the polymer coating of the TNT sheet with the surface stably combined with the iodine.
As a further improvement of the invention, the preparation method of the TNT sheet with the nanotube on the surface comprises the following steps:
mixing ammonium fluoride, water and glycerol to prepare electrolyte; adopting a constant voltage direct current anodic oxidation method to make a Ti sheet as an anode and a platinum sheet as a cathode; and (3) reacting for 1.5-20 hours at a voltage of 30-80V to form a Ti nanotube array, taking out, cleaning, airing, calcining at 400-450 ℃ in a tube furnace for 3-5 hours, naturally cooling, and ultrasonically removing surface impurities to obtain the TNT sheet with the nanotubes on the surface.
As a further improvement of the invention, the inner diameter of the Ti nanotube is 100-200 nm.
As a further improvement of the invention, the molar ratio of the 1-vinyl-2-pyrrolidone to the crosslinking agent is (0.8:1) to (3: 1).
As a further improvement of the invention, the thickness of the film is 50-100 nm.
As a further improvement of the present invention, the substrate temperature during deposition is controlled by a water circulation system and monitored by a thermocouple to prevent damage to the properties of the substrate material.
As a further improvement of the invention, the nickel-chromium wire is arranged at the position of 2-3 cm above the reaction platform and is heated to the temperature of 200-400 ℃.
As a further improvement of the present invention, the pressure in the reactor is controlled to 0.1to 1.0Torr by a throttle valve, and the flow rates of the monomers participating in the reaction are controlled by mass flow controllers.
As a further improvement of the invention, I2The NaI solution is prepared from I with the mass concentration of 1g/mL2The solution and NaI with the mass concentration of 0.5g/mL are prepared; the temperature of the shaking table is 25-37 ℃, the shaking table is protected from light, and the shaking speed is 100-200 r/min.
The titanium nanotube iodine coating prepared by the method is used as the surface antibacterial application of the biomedical Ti material.
Compared with the prior art, the invention has the following technical effects and advantages:
compared with the traditional liquid-phase polymer coating preparation method, the polymer chemical vapor deposition method is a green novel functional polymer coating preparation method, combines the traditional liquid-phase free radical polymerization reaction and chemical vapor deposition technology, gasifies and introduces an initiator and functional monomers required by polymerization into a cavity, induces the initiator to crack at a lower heating temperature to generate free radicals, enables the monomers to generate polymer coatings through the free radical polymerization reaction and deposit on substrates with various shapes, synthesizes uniform films, and further finely modifies the micro-nano structure on the surface of the material. The high molecular chemical vapor deposition reaction process does not use organic solvent harmful to human body, and P (VP-co-EGDA) is plated on the surface of the medical material to promote the biocompatibility of the material. According to the invention, a P (VP-co-EGDA) film is prepared on the surface of a Ti material with a nanotube on the surface by a high molecular chemical vapor deposition method, I is fixed on the surface of the material after being complexed with I to form TNT-P (VP-co-EGDA) -I, and the slow release anti-infection of I is realized and the infection of drug-resistant bacteria is inhibited by releasing I for sterilization.
Preferably, the thickness of the coating layer is precisely controlled by monitoring the coating preparation process through a laser interferometer, and in the present invention, the thickness of P (VP-co-EGDA) is controlled to be 50-100 nm.
The method adopts a constant-voltage direct-current anodic oxidation method to prepare The Nanotube (TNT) on the surface of a Ti material, then synthesizes P (VP-co-EGDA) on the surface of the TNT in one step by a high-molecular chemical vapor deposition method, and finally forms a stable coating of P (VP-co-EGDA) -I on the surface of the TNT by complexing with I.
TNT-P (VP-co-EGDA) -I kills pathogenic microorganisms including drug-resistant bacteria through the release of I, and the obtained product can be applied to the surface of a Ti implant, reduces microbial infection and has high application value.
Drawings
FIG. 1 is a schematic structural diagram of TNT-P (VP-co-EGDA) -I obtained in example 1 of the present invention;
FIG. 2 is FTIR spectra of P (VP-co-EGDA) thin films obtained in comparative example 2 and example 1 of the present invention;
FIG. 3 is a photograph showing the actual products of TNT, TNT-P (VP-co-EGDA) -I obtained in comparative examples 1, 2 and 3 and example 1;
FIG. 4 is a scanning electron micrograph of TNT and TNT-P (VP-co-EGDA) obtained in comparative examples 1 and 2 and example 1 according to the present invention;
FIG. 5 is a zone analysis of inhibition of TNT, TNT-P (VP-co-EGDA) -I against E.coli and methicillin-resistant Staphylococcus aureus obtained in comparative examples 1, 2 and 3 and example 1 of the present invention;
FIG. 6 shows the bactericidal analysis of Escherichia coli and methicillin-resistant Staphylococcus aureus after reacting TNT and TNT-P (VP-co-EGDA) obtained in comparative examples 1 and 3 and example 1, respectively, with I and rinsing with deionized water.
Detailed Description
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. The voltage is 30-80V, the reaction is 1.5-20h, and the Ti nanotube array is formed. And after the anode oxidation is finished, taking out the sample, washing with deionized water, airing, calcining in a tube furnace at 400-450 ℃ for 3-5 h, naturally cooling to improve the binding force of the Ti nanotube array and the substrate Ti sheet, and then performing ultrasonic treatment for 120s to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
And (3) placing the TNT substrate on a sample table of a high-molecular chemical vapor deposition reactor. The initiator of di-tert-butyl peroxide (TBP), the functional monomer of 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent of Ethylene Glycol Diacrylate (EGDA) are heated to 30, 80 and 65 ℃ respectively, and gasified and flowed into the reactor, and the flow rate of each monomer is controlled by a mass flow controller. The nickel-chromium wires are arranged in order at a position of 2-3 cm above the reaction platform and heated to 200-400 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. Deposition ofThe substrate temperature was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ during the process to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.1to 1.0Torr by a throttle valve. The thickness of the film is controlled to be 50nm-100nm through the monitoring of a real-time laser interferometer, and when the thickness of a P (VP-co-EGDA) coating film reaches the expected requirement, the inflow of an initiator TBP and monomers VP and EGDA is stopped. And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers. Sample in2NaI solution (1g/mL I)2And 0.5g/mL NaI), at 25-37 ℃ and 100-200r/min, and complexing with iodine for 0.5-4h in a dark place.
The inner diameter of the TNT is 100-200 nm.
The P (VP-co-EGDA) is 50-100nm, and the VP/EGDA monomer molar ratio is (0.8:1) - (3: 1).
P (VP-co-EGDA) film material in I2NaI solution (1g/mL I)2And 0.5g/mL of NaI), the complexing time with iodine is not less than 0.5 h.
The present invention will be described in further detail with reference to the following embodiments and the accompanying drawings.
Example 1
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 12h at a voltage of 60V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at the temperature of 420 ℃ for 4 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120s to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator di-tert-butyl peroxide (TBP), the functional monomer 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 1.25: 1. The nickel chromium wires were aligned 2.5cm above the reaction table and heated to 250 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.25Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 50nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping away from light at 37 ℃ for 1h, and carrying out complex reaction with iodine.
Comparative example 1
Preparation of TNT: cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 12h at a voltage of 60V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at the temperature of 420 ℃ for 4 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120s to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
Comparative example 2
Preparation of P (VP-co-EGDA) film: the TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator di-tert-butyl peroxide (TBP), the functional monomer 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 1.25: 1. The nickel chromium wires were aligned 2.5cm above the reaction table and heated to 250 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.25Torr by a throttle valve.
The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 50nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped. And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
Comparative example 3
Preparation of TNT-P (VP-co-EGDA) -I: adding TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping away from light at 37 ℃ for 1h, and carrying out complex reaction with iodine.
After the reaction is finished, the sample is soaked and washed by deionized water to remove unbound I, and the sample is dried and subjected to antimicrobial detection.
As shown in fig. 2, is the inventionFT-IR spectra of the copolymer P (VP-co-EGDA) obtained in comparative example 2 and example 1; c ═ O derived from VP in polymer film P (VP-co-EGDA) was 1662cm-1And C ═ O from EGDA at 1733cm-1and-OH in water molecules originating from PVP absorption at 3460cm-1As the central broad peak, the successful preparation of the P (VP-co-EGDA) film is proved.
As shown in FIG. 3, the color analysis of the TNT, TNT-P (VP-co-EGDA) and TNT-P (VP-co-EGDA) -I obtained in comparative examples 1, 2 and 3 and example 1 according to the present invention was carried out by taking photographs of the samples. TNT and TNT- (VP-co-EGDA) are the color of the Ti sheet; in I2After reaction with NaI solution, the TNT- (VP-co-EGDA) -I surface was brown.
As shown in FIG. 4, SEM photographs of TNT and TNT- (VP-co-EGDA) obtained in comparative examples 1 and 2 and example 1 of the present invention; FIG. 4 shows that the inner diameter of TNT is about 120-150 nm; after coating (VP-co-EGDA), the TNT surface becomes flat and the inner diameter is reduced, which proves that the preparation of the TNT-P (VP-co-EGDA) is successful.
As shown in fig. 5, TNT-P (VP-co-EGDA) -I obtained in comparative examples 1, 2, and 3 and example 1 of the present invention were analyzed for zone inhibition of escherichia coli (e.coli) and methicillin-resistant staphylococcus aureus (MRSA): the TNT and the TNT-P (VP-co-EGDA) have no bactericidal effect, only the TNT-P (VP-co-EGDA) -I has obvious bactericidal activity on E.coli and MRSA, and after the I is released for sterilization, the color of the TNT-P (VP-co-EGDA) -I is restored to the color of the Ti sheet from brown.
As shown in fig. 6, after TNT and TNT-P (VP-co-EGDA) obtained in comparative examples 1 and 3 and example 1 of the present invention were complexed with I, respectively, and washed with deionized water, they were analyzed for sterilization of escherichia coli (e.coli) and methicillin-resistant staphylococcus aureus (MRSA): the combination of TNT and I is unstable, and after washing, the sterilization effect on E.coli and MRSA is avoided; the TNT-P (VP-co-EGDA) can be stably combined with I, and after being washed by water, the TNT-P (VP-co-EGDA) -I has obvious bactericidal effects on E.coli and MRSA. Both scanning electron microscopy and bacterial plating demonstrated. The TNT-P (VP-co-EGDA) can stably fix the I, thereby realizing the slow-release sterilization of the I on the TNT.
Example 2
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 1.5h at a voltage of 80V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at 400 ℃ for 3 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120 seconds to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator of di-tert-butyl peroxide (TBP), the functional monomer of 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent of Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, and gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 1: 1. The nickel chromium wires were aligned 3cm above the reaction table and heated to 300 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.2Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 100nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping out of the sun at 30 ℃, 100r/min, and carrying out complex reaction with iodine for 0.5h to obtain the polymer coating with the TNT sheet surface stably combined with iodine.
Example 3
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 20h at the voltage of 30V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at 440 ℃ for 4 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120 seconds to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator of di-tert-butyl peroxide (TBP), the functional monomer of 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent of Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, and gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 2: 1. The nickel chromium wires were aligned 2.5cm above the reaction table and heated to 270 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.15Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 60nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping out of the sun at 28 ℃, 150r/min, and carrying out a complexing reaction with iodine for 3h to obtain the polymer coating with the TNT sheet surface stably combined with iodine.
Example 4
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 18h at a voltage of 50V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at 450 ℃ for 4 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120 seconds to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator di-tert-butyl peroxide (TBP), the functional monomer 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 0.8: 1. The nickel chromium wires were aligned 2.5cm above the reaction table and heated to 280 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.8Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 90nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping out of the sun at 35 ℃, 100r/min, and carrying out a complexing reaction with iodine for 2h to obtain the polymer coating with the TNT sheet surface stably combined with iodine.
Example 5
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 500r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 18h at a voltage of 50V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at the temperature of 420 ℃ for 3 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120 seconds to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator of di-tert-butyl peroxide (TBP), the functional monomer of 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent of Ethylene Glycol Diacrylate (EGDA) are heated to 30, 80 and 65 ℃ respectively, and gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 3: 1. The nickel chromium wires were aligned 2.5cm above the reaction table and heated to 400 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 0.1Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 80nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping out of the sun at 25 ℃, 120r/min, and carrying out a complexing reaction with iodine for 4h to obtain the polymer coating with the TNT sheet surface stably combined with iodine.
Example 6
The invention relates to a method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method, which comprises the following steps:
cutting a pure titanium (Ti) sheet into rectangular samples with certain sizes, and polishing the samples by using metallographic abrasive paper of No. 400, No. 800 and No. 2000 respectively until the surfaces are smooth and have no scratches. Washing the abrasive dust with deionized water, then ultrasonically cleaning with acetone to remove oil stains on the surface of the titanium, finally cleaning with deionized water, and drying for later use.
An electrolyte was prepared by mixing 1.26g of ammonium fluoride, 20ml of ultrapure water and 180ml of glycerol. Adding a magnetic stirrer into the electrolyte, stirring on a magnetic stirrer at the rotating speed of 800r/min for 1h to uniformly mix the electrolyte.
And (3) adopting a constant-voltage direct-current anodic oxidation method to make the pretreated Ti sheet as an anode and the platinum sheet as a cathode. And reacting for 18h at a voltage of 70V to form the Ti nanotube array. And after the anode oxidation is finished, taking out the sample, washing the sample by using deionized water, airing the sample, calcining the sample in a tube furnace at 450 ℃ for 5 hours, naturally cooling the sample to improve the binding force between the Ti nanotube array and the substrate Ti sheet, and then carrying out ultrasonic treatment for 120 seconds to remove surface impurities to obtain the TNT sheet with the nanotubes on the surface.
The TNT sheet is used as a substrate and is placed on a sample table of a high molecular chemical vapor deposition reactor. The initiator of di-tert-butyl peroxide (TBP), the functional monomer of 1-vinyl-2-pyrrolidone (VP) and the cross-linking agent of Ethylene Glycol Diacrylate (EGDA) are heated to 30 ℃, 80 and 65 ℃ respectively, and gasified and flowed into the reactor, the flow rate of each monomer is controlled by a mass flow controller, and the molar ratio of VP to EGDA monomer is 2: 1. The nickel chromium wires were aligned 2cm above the reaction table and heated to 200 ℃. And (3) allowing an initiator TBP to enter a reactor, heating and decomposing the initiator TBP by a nickel-chromium wire to generate free radicals, then initiating a free radical chain polymerization reaction, and depositing the synthesized high polymer on the TNT sheet. The substrate temperature during deposition was controlled by a water circulation system and monitored by a thermocouple at 35 ℃ to ensure that the properties of the substrate material were not compromised. The pressure in the reactor was controlled at 1Torr by a throttle valve. The film thickness was monitored by a real-time laser interferometer, and when the thickness of the P (VP-co-EGDA) coating reached 100nm, the inflow of the initiator TBP and the monomers VP and EGDA was stopped.
And after the reaction is finished, soaking a sample prepared by the high molecular chemical vapor deposition with deionized water to remove residual monomers.
TNT-P (VP-co-EGDA) in I2NaI solution (1g/mL I)2And 0.5g/mL NaI), keeping out of the sun at 37 ℃, 200r/min, and carrying out a complexing reaction with iodine for 2h to obtain the polymer coating with the TNT sheet surface stably combined with iodine.
Application example 1
Sterilization analysis of TNT-P (VP-co-EGDA) -I prepared in inventive example 1: the TNT-P (VP-co-EGDA) -I still has remarkable bactericidal activity after being soaked in water for 2 days and 5 days, and the P (VP-co-EGDA) film coated on the TNT surface can stably fix I on the TNT surface, can kill microorganisms by slowly releasing I, and can be applied to the surface of a medical Ti implant.
In conclusion, the invention provides a method for preparing the titanium nanotube iodine coating by the chemical vapor deposition method simply and efficiently and application thereof. Preparing a Titanium Nano Tube (TNT) with controllable tube diameter and tube length on the surface of a titanium material by a constant-pressure direct-current anodic oxidation method, then copolymerizing and depositing 1-vinyl-2-pyrrolidone (VP) and cross-linked molecular Ethylene Glycol Diacrylate (EGDA) on the surface of the TNT by a high-molecular chemical vapor deposition method under a mild reaction condition to form TNT-P (VP-co-EGDA), then complexing with iodine (I) under the mild condition to prepare TNT-P (VP-co-EGDA) -I, and fixing I on the surface of the TNT, so that the titanium material has a function of killing microorganisms and has an obvious effect on drug-resistant bacteria. The insolubility of P (VP-co-EGDA) on the surface of TNT is beneficial to fixing I on the surface of a medical titanium instrument, so that the infection caused by bacteria on the surface is reduced, and the drug resistance is not generated.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.

Claims (10)

1. A method for preparing a titanium nanotube iodine coating by a chemical vapor deposition method is characterized by comprising the following steps:
forming a Ti nanotube array on the surface of a Ti sheet by adopting a constant-voltage direct-current anodic oxidation method, and then calcining and ultrasonically treating to obtain a TNT sheet with nanotubes on the surface;
the TNT sheet with the nanotube on the surface is placed on a sample table of a reactor for chemical vapor deposition, and then an initiator di-tert-butyl peroxide, 1-vinyl-2-pyrrolidone and a cross-linking agent ethylene glycol diacrylate are respectively heated to be gasified and flow into the reactor;
arranging a nickel-chromium wire above the reaction table and heating to a desired temperature; the initiator enters a reactor, is heated and decomposed by a nickel-chromium wire to generate free radicals, further initiates the free radical chain type polymerization reaction of the 1-vinyl-2-pyrrolidone and the cross-linking agent, and the synthesized high polymer is deposited on the TNT to form a film; when the film thickness reaches the expected requirement, the inflow of the 1-vinyl-2-pyrrolidone and the cross-linking agent is stopped; after the reaction is finished, washing the sample with water to remove residual monomers, and airing to obtain the TNT sheet with the surface modified with the polymer film;
immersing the TNT sheet of the surface modified polymer film in the solution I2And putting the TNT/NaI solution on a shaking bed to perform a complex reaction of the polymer film and iodine, then taking out and washing to remove free iodine on the surface, and airing to obtain the polymer coating of the TNT sheet with the surface stably combined with the iodine.
2. The method for preparing the iodine coating of the titanium nanotube by the chemical vapor deposition method according to claim 1, wherein the TNT sheet with the nanotube on the surface is prepared by the following steps:
mixing ammonium fluoride, water and glycerol to prepare electrolyte; adopting a constant voltage direct current anodic oxidation method to make a Ti sheet as an anode and a platinum sheet as a cathode; reacting under the condition of voltage of 30-80V to form a Ti nanotube array, taking out, cleaning and airing after anode oxidation is finished, calcining for 3-5 h at 400-450 ℃ in a tubular furnace, naturally cooling, and ultrasonically removing surface impurities to obtain the TNT sheet with the nanotubes on the surface.
3. The method as claimed in claim 1, wherein the inner diameter of the nanotube on the surface of the Ti plate is 100-200 nm.
4. The method for preparing the iodine coating of the titanium nanotube by the chemical vapor deposition method according to claim 1, wherein the molar ratio of the 1-vinyl-2-pyrrolidone to the cross-linking agent is (0.8:1) - (3: 1).
5. The method for preparing the iodine coating of the titanium nanotube by the chemical vapor deposition method according to claim 1, wherein the thickness of the film is 50-100 nm.
6. The method of claim 1, wherein the substrate temperature during deposition is controlled by a water circulation system and monitored by a thermocouple, and the temperature does not harm the properties of the substrate material.
7. The method as claimed in claim 1, wherein the Ni-Cr wires are arranged 2-3 cm above the reaction platform and heated to 200-400 ℃.
8. The method of preparing iodine-coated titanium nanotubes by chemical vapor deposition as claimed in claim 1, wherein the pressure of the reactor is controlled by a throttle valve at 0.1to 1.0Torr and the flow rate of each monomer participating in the reaction is controlled by a mass flow controller.
9. The method for preparing the iodine coating of the titanium nanotube by the chemical vapor deposition method according to claim 1, wherein I is2The NaI solution is prepared from I with the mass concentration of 1g/mL2The solution and NaI with the mass concentration of 0.5g/mL are prepared; the temperature of the shaking table is 25-37 ℃, the shaking table is protected from light, and the shaking speed is 100-200 r/min.
10. The use of the iodine coating of titanium nanotubes prepared by the method of any one of claims 1to 9 as an antimicrobial surface of biomedical Ti materials.
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