CN113005407A - Preparation method of stainless steel material plated with diamond-like carbon antibacterial film - Google Patents

Preparation method of stainless steel material plated with diamond-like carbon antibacterial film Download PDF

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CN113005407A
CN113005407A CN201911313924.6A CN201911313924A CN113005407A CN 113005407 A CN113005407 A CN 113005407A CN 201911313924 A CN201911313924 A CN 201911313924A CN 113005407 A CN113005407 A CN 113005407A
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stainless steel
silver
diamond
steel material
film
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CN113005407B (en
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江晓红
方嘉林
刘昱玮
马婷婷
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Nanjing University of Science and Technology
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Nanjing University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0605—Carbon

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention discloses a preparation method of a stainless steel material plated with a diamond-like carbon antibacterial film. According to the method, graphite is used as a film forming material, a silver rod is inserted into the cross section of a graphite target material, the graphite and silver are simultaneously evaporated by adopting a vacuum cathodic arc plasma evaporation technology, the graphite and the silver are deposited on the surface of a stainless steel material under the action of a magnetic field, and nano-silver is uniformly doped on the surface of the stainless steel material. The stainless steel material plated with the diamond-like carbon antibacterial film prepared by the method has excellent antibacterial performance and wear resistance.

Description

Preparation method of stainless steel material plated with diamond-like carbon antibacterial film
Technical Field
The invention relates to a preparation method of a stainless steel material plated with a diamond-like carbon antibacterial film, belonging to the technical field of antibacterial material preparation.
Background
The traditional stainless steel scalpel has the problems that bacteria are easily infected in the storage and transportation process, the disinfection process is complicated before use, and the like. The diamond-like antibacterial film is loaded on the surface of the scalpel, so that active sterilization is easy to realize in the transportation and storage processes, the possibility of germ infection in the operation process is reduced, bacteria cannot generate drug resistance, and the use of antibiotics is reduced.
Graphite as a widely used material has the advantages of wide source, low price, reproducibility and the like, but the diamond-like carbon film made of graphite also has the problems of no antibacterial property, easy shedding and the like. Although silver ions have a bactericidal effect, the silver ions are difficult to be loaded and fixed in a solid, particularly on a metal surface, and the application of the silver ions is greatly limited. The adhesion degree can be improved by compounding diamond-like carbon with other metal materials.
The Neei-Kongyin et al adopts a non-equilibrium magnetron sputtering technology to deposit a non-doped diamond-like carbon (DLC) film and Ti-doped diamond-like carbon (Ti2DLC) films with different contents on a SCM415 carburized and quenched steel substrate with a mirror polished surface. The film-substrate bonding strength is monotonously increased along with the doping of Ti. They believe that as Ti content increases, TiC nanocrystals (nieoni-dynasty-yin, sierra prume, the silk-juan, the courser, the basic properties of the unbalanced magnetron sputtering Ti-doped diamond-like thin film, material heat treatment journal 2008,29(03): 148-. Although the above method improves the bonding force between the diamond-like thin film and the metal, it has a problem of no antibacterial property.
Silver ions are used as a natural antibacterial substance, and have great potential advantages in the field of biomedical films due to the excellent characteristics of no toxicity, no harm, bacteriostasis, small harm to human bodies and the like. The method is characterized in that the method adopts a low-power electron beam evaporation method, silver nitrate powder is used as a silver source, polymethyl methacrylate, polyethylene and polylactic acid are respectively used as polymer matrix materials, and composite films with different polymer groups doped with silver are prepared (in Sunjing, the research on a film forming mechanism and the performance of the composite films with metal polymer groups deposited by the electron beam evaporation method [ D ]. Nanjing university of science and technology, 2017.). However, the composite film still has the problems of poor wear resistance and easy breakage in the storage process. The Chinese patent application 201910482299.1 adopts a sputtering method to prepare the silver-containing diamond-like antibacterial film, but the cost of the silver target is high, and the adopted sputtering coating technology has the conditions of uneven coating and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a stainless steel material plated with a diamond-like carbon antibacterial film and capable of resisting storage abrasion. According to the method, a diamond-like film replaces a traditional organic polymer film, a silver rod is inserted into a graphite target, silver with antibacterial performance is dissolved in the graphite target as a solute of a solid solution, and a layer of diamond-like silver-doped film is plated on the surface of stainless steel.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the stainless steel material plated with the diamond-like carbon antibacterial film comprises the following specific steps:
step 1, inserting silver rods into the cross section of a graphite target material, and distributing the silver rods at the vertexes of an equilateral triangle concentric with the cross section of the graphite and having the side length of 1cm to prepare a silver-doped graphite target material;
and 2, putting the stainless steel material subjected to ultrasonic cleaning into a vacuum cathode arc plasma evaporation cavity, vacuumizing, and plating a film on the stainless steel material by adopting a vacuum cathode arc plasma evaporation method to obtain the stainless steel material plated with the diamond-like antibacterial film.
Preferably, in step 1, the purity of the silver rod is 99.99%.
Preferably, in step 1, the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0724: 1.
preferably, in step 2, the stainless steel material may be a medical scalpel.
Preferably, in the step 2, ultrasonic cleaning of the stainless steel material is performed for 5-10 minutes by using ethanol, then ultrasonic cleaning is performed for 5-10 minutes by using distilled water, and finally ultrasonic cleaning is performed by using ethanol, wherein the ultrasonic frequency is 5 Hz.
Preferably, in the step 2, the number of plating is 1000-2000.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method is simple, convenient and quick, does not add any irritant or toxic substance, is convenient for large-scale production, and accords with the development trend of medical instruments;
(2) the diamond-like film is adopted to replace a high molecular organic matter, so that the wear resistance of the film can be improved;
(3) according to the invention, the nano silver which is harmless to human bodies and has strong antibacterial property is added into the diamond-like carbon film, so that the binding force of the composite film can be improved on one hand, and the antibacterial property of the composite film can be improved on the other hand;
(4) according to the invention, the silver rods are inserted into the carbon target, and the positions and distances of the three silver rods are strictly controlled, so that uniform and stable antibacterial nano silver is physically and stably deposited on the surface of the stainless steel in a vapor phase manner, a large silver target does not need to be specially manufactured, the utilization rate of the silver is greatly improved, and the fund is saved.
Drawings
FIG. 1 is a graph showing the antibacterial effect of the diamond-like antibacterial film prepared by doping three silver rods on Staphylococcus aureus in example 1;
FIG. 2 is a graph showing the antibacterial effect of the silver-free diamond-like antibacterial film prepared in comparative example 1 on Staphylococcus aureus;
FIG. 3 is a graph showing the antibacterial effect of the diamond-free stainless steel sheet manufactured in comparative example 2 against Staphylococcus aureus;
FIG. 4 is a graph showing the antibacterial effect of the diamond-like antibacterial film prepared by doping seven silver rods on Staphylococcus aureus in comparative example 3. FIG. 5 is an XPS analysis of the diamond-like carbon film of example 1.
FIG. 6 is an electron micrograph of the diamond-like thin film of example 1.
FIG. 7 is an EDS scan of silver in the diamond-like film obtained in example 1.
Fig. 8 is an XPS analysis chart of the diamond-like thin film of comparative example 3.
FIG. 9 is an EDS scan of silver in the diamond-like film made in comparative example 3.
Fig. 10 is an XPS analysis chart of the diamond-like thin film of comparative example 3.
Detailed Description
The present invention will be described in further detail below with reference to examples and the accompanying drawings.
Example 1
Three cylindrical silver rods with the length of 5mm and the diameter of 3mm are taken. Inserting silver rods into the cross section of a graphite target material with the length of 10cm and the diameter of 3cm, distributing the silver rods at the vertex of an equilateral triangle concentric with the cross section of the graphite and with the side length of 1cm, wherein the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0724: 1, preparing the silver-doped graphite target material. Taking a stainless steel sheet with the square centimeter about 1 square centimeter, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, carrying out ultrasonic treatment for 5 minutes, taking the stainless steel sheet, putting the stainless steel sheet into a 50ml beaker containing 20ml of purified water, carrying out ultrasonic treatment for 5 minutes, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, and carrying out ultrasonic treatment for 5 minutes. Taking out the stainless steel sheet, airing, putting into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a silver-doped graphite target material, plating films for 2000 times by using 5Hz to obtain a film coating material, and performing an antibacterial experiment on the obtained film material.
Comparative example 1
Taking a stainless steel sheet with the square centimeter about 1 square centimeter, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, carrying out ultrasonic treatment for 5 minutes, taking out the stainless steel sheet, putting the stainless steel sheet into a 50ml beaker containing 20ml of purified water, carrying out ultrasonic treatment for 5 minutes, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, and carrying out ultrasonic treatment for 5 minutes. Taking out the stainless steel sheet, air drying, placing into Vactime-DLC vacuum cathode arc plasma evaporation equipment, vacuumizing, using a graphite target material which does not contain silver and has the length of 10cm and the diameter of 3cm, coating for 2000 times by using 5Hz to obtain a coating material, and performing an antibacterial experiment on the obtained film material.
Comparative example 2
Taking a stainless steel sheet with the square centimeter about 1 square centimeter, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, carrying out ultrasonic treatment for 5 minutes, taking out the stainless steel sheet, putting the stainless steel sheet into a 50ml beaker containing 20ml of purified water, carrying out ultrasonic treatment for 5 minutes, putting the stainless steel sheet into a 50ml beaker containing 20ml of 99% ethanol, and carrying out ultrasonic treatment for 5 minutes. And taking out the stainless steel sheet, airing, and carrying out an antibacterial experiment on the obtained material.
Comparative example 3
The comparative example is basically the same as example 1, the only difference is that the graphite target material doped with silver is replaced, the distribution of seven silver rods in the graphite target material is changed into a hexagonal vertex with the side length of 8mm and a hexagonal center, and the ratio of the exposed surface area of silver to the exposed surface area of graphite is 0.1848: 1.
TABLE 1 antibacterial zone size of diamond-like antibacterial film
Diamond-like antibacterial film formula Diameter/mm of bacteriostatic circle
Example 1 Diamond-like carbon film doped with three silver rods 32
Comparative example 1 Diamond-like thin film undoped silver 0
Comparative example 2 Film of no diamond 0
Comparative example 3 Diamond-like carbon film doped with seven silver rods 0
FIG. 1 is a graph showing the antibacterial effect of the diamond-like antibacterial film prepared by doping three silver rods on Staphylococcus aureus in example 1; FIG. 2 is a graph showing the antibacterial effect of the silver-free diamond-like antibacterial film prepared in comparative example 1 on Staphylococcus aureus; FIG. 3 is a graph showing the antibacterial effect of the diamond-free stainless steel sheet manufactured in comparative example 2 against Staphylococcus aureus; FIG. 4 is a graph showing the antibacterial effect of the diamond-like antibacterial film prepared by doping seven silver rods on Staphylococcus aureus in comparative example 3.
As shown in Table 1 and FIG. 1, the diamond-like antibacterial film obtained in example 1 has a zone of inhibition, and comparative examples 1 and 2 have no antibacterial property. Comparing example 1 with comparative examples 1 and 3,doping silver into diamond-like films can impart antimicrobial properties to the film, but silver particles are too large and have no antimicrobial properties. The reason is that the silver is only uniformly distributed in the diamond-like carbon film and becomes small nano silver particles, the nano silver particles have extremely large specific surface area, and free silver ions, Ag, are easily generated+The bacterium is positively charged and can generate electrostatic attraction with negatively charged bacteria, the bacteria have respiration enzyme and have sulfhydryl protease, the bacteria are preferentially combined with silver ions after meeting the silver ions, the sulfhydryl protease is inactivated and loses nutrition, and then is broken, and the bacteria lose the division reproductive capacity and die. Comparing example 1 and comparative example 2, it is known that the diamond-like film itself has no antibacterial property. Referring to fig. 1, 2, 3 and 4, the diamond-like carbon film doped with three silver rods has an antibacterial effect.
FIG. 5 is an XPS analysis of the diamond-like film of example 1 showing that the sample contained 2% silver. FIG. 6 is an electron microscope of the diamond-like thin film of example 1, and it can be seen that the sample contains nano silver particles. Fig. 7 is an EDS scan of silver in the diamond-like thin film obtained in example 1, and it can be seen that nano silver particles are uniformly distributed in the diamond-like thin film. Fig. 8 is an XPS analysis of the diamond-like thin film of comparative example 3, and it can be seen that silver is present in the micrometer scale without nano silver particles. Fig. 9 is an EDS scan of silver in the diamond-like thin film obtained in comparative example 3, and it can be seen that the silver distribution is not uniform. FIG. 10 is an XPS analysis of the diamond-like film of comparative example 3, showing that the sample contained 2% silver.

Claims (6)

1. The preparation method of the stainless steel material plated with the diamond-like carbon antibacterial film is characterized by comprising the following specific steps of:
step 1, inserting silver rods into the cross section of a graphite target material, and distributing the silver rods at the vertexes of an equilateral triangle concentric with the cross section of the graphite and having the side length of 1cm to prepare a silver-doped graphite target material;
and 2, putting the stainless steel material subjected to ultrasonic cleaning into a vacuum cathode arc plasma evaporation cavity, vacuumizing, and plating a film on the stainless steel material by adopting a vacuum cathode arc plasma evaporation method to obtain the stainless steel material plated with the diamond-like antibacterial film.
2. The method according to claim 1, wherein the silver rod has a purity of 99.99% in step 1.
3. The preparation method according to claim 1, wherein in the step 1, the ratio of the total exposed sectional area of the three silver rods to the exposed sectional area of the graphite is 0.0724: 1.
4. the method according to claim 1, wherein in step 2, the stainless steel material is a medical scalpel.
5. The preparation method according to claim 1, wherein in the step 2, the stainless steel material is ultrasonically cleaned by ethanol for 5-10 minutes, then ultrasonically cleaned by distilled water for 5-10 minutes, and finally ultrasonically cleaned by ethanol with the ultrasonic frequency of 5 Hz.
6. The method according to claim 1, wherein the number of plating in step 2 is 1000 to 2000.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022102168A1 (en) 2022-01-31 2023-08-03 Grohe Ag Process for coating a substrate and use of a target for coating a substrate

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CN102703858A (en) * 2012-06-13 2012-10-03 中国地质大学（北京） Metallic DLC (diamond-like carbon) film preparation method
CN106507848B (en) * 2011-10-08 2014-03-19 成都飞机工业（集团）有限责任公司 A kind of diamond-film-like depositing operation
CN109706503A (en) * 2019-01-20 2019-05-03 中国科学院宁波材料技术与工程研究所 A kind of the antibacterial wear-resistant coating and preparation method on Titanium base surface
CN110117777A (en) * 2019-06-04 2019-08-13 东莞市和荣纳米技术有限公司 A kind of preparation method of the diamond-like coating with antibacterial and high-wear resistance

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CN106507848B (en) * 2011-10-08 2014-03-19 成都飞机工业（集团）有限责任公司 A kind of diamond-film-like depositing operation
CN102703858A (en) * 2012-06-13 2012-10-03 中国地质大学（北京） Metallic DLC (diamond-like carbon) film preparation method
CN109706503A (en) * 2019-01-20 2019-05-03 中国科学院宁波材料技术与工程研究所 A kind of the antibacterial wear-resistant coating and preparation method on Titanium base surface
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102022102168A1 (en) 2022-01-31 2023-08-03 Grohe Ag Process for coating a substrate and use of a target for coating a substrate

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