CN112972780B - Biliary tract stent surface nano coating and preparation method thereof - Google Patents
Biliary tract stent surface nano coating and preparation method thereof Download PDFInfo
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- CN112972780B CN112972780B CN202110451950.6A CN202110451950A CN112972780B CN 112972780 B CN112972780 B CN 112972780B CN 202110451950 A CN202110451950 A CN 202110451950A CN 112972780 B CN112972780 B CN 112972780B
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- 210000003445 biliary tract Anatomy 0.000 title claims abstract description 27
- 239000002103 nanocoating Substances 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 13
- 238000000576 coating method Methods 0.000 claims abstract description 43
- 239000011248 coating agent Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims description 55
- 238000004544 sputter deposition Methods 0.000 claims description 45
- 239000002245 particle Substances 0.000 claims description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 36
- 238000004140 cleaning Methods 0.000 claims description 27
- 239000007789 gas Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 23
- 229910002701 Ag-Co Inorganic materials 0.000 claims description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000005554 pickling Methods 0.000 claims description 18
- 238000005498 polishing Methods 0.000 claims description 16
- 239000002131 composite material Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 9
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- -1 polyethylene Polymers 0.000 claims description 5
- 239000013077 target material Substances 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 238000005238 degreasing Methods 0.000 claims 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 13
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 9
- 231100000331 toxic Toxicity 0.000 abstract description 9
- 230000002588 toxic effect Effects 0.000 abstract description 9
- 229910052709 silver Inorganic materials 0.000 abstract description 6
- 239000004332 silver Substances 0.000 abstract description 6
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 230000001580 bacterial effect Effects 0.000 description 8
- 238000007709 nanocrystallization Methods 0.000 description 8
- 239000007769 metal material Substances 0.000 description 7
- 241000699670 Mus sp. Species 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 210000000941 bile Anatomy 0.000 description 3
- 210000002490 intestinal epithelial cell Anatomy 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 208000035143 Bacterial infection Diseases 0.000 description 2
- 208000022362 bacterial infectious disease Diseases 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 206010004593 Bile duct cancer Diseases 0.000 description 1
- 206010061902 Pancreatic neoplasm Diseases 0.000 description 1
- 208000031481 Pathologic Constriction Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000008436 biogenesis Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 230000005779 cell damage Effects 0.000 description 1
- 208000037887 cell injury Diseases 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 210000001198 duodenum Anatomy 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000000968 intestinal effect Effects 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 208000015486 malignant pancreatic neoplasm Diseases 0.000 description 1
- 208000037819 metastatic cancer Diseases 0.000 description 1
- 208000011575 metastatic malignant neoplasm Diseases 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 201000002528 pancreatic cancer Diseases 0.000 description 1
- 208000008443 pancreatic carcinoma Diseases 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 208000037803 restenosis Diseases 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 208000037804 stenosis Diseases 0.000 description 1
- 230000036262 stenosis Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/08—Materials for coatings
- A61L31/082—Inorganic materials
- A61L31/088—Other specific inorganic materials not covered by A61L31/084 or A61L31/086
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L31/16—Biologically active materials, e.g. therapeutic substances
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/06—Alloys based on silver
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- 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
- C23C14/14—Metallic material, boron or silicon
- C23C14/20—Metallic material, boron or silicon on organic substrates
- C23C14/205—Metallic material, boron or silicon on organic substrates by cathodic sputtering
-
- 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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- 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
- C23C14/58—After-treatment
- C23C14/5886—Mechanical treatment
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/45—Mixtures of two or more drugs, e.g. synergistic mixtures
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/60—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a special physical form
- A61L2300/606—Coatings
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Abstract
In order to overcome the toxic and side effects of the nano-silver coating on the surface of the biliary tract stent, part of metal element cobalt replaces metal element silver, and the antibacterial performance of the part of coating is sacrificed, so that the safety of the biliary tract stent coating material is greatly improved. Research shows that when the cobalt content in the coating is 29%, the antibacterial performance and the toxic and side effects of the stent coating achieve the most excellent balance effect.
Description
Technical Field
The invention relates to the field of nano coatings, in particular to a biliary tract stent surface nano coating and a preparation method thereof.
Background
The biliary system has the functions of secretion, storage, concentration and bile delivery, and has an important regulation effect on bile discharge into duodenum, but biliary obstruction can be caused by malignant tumors such as biliary cancer, liver cancer, pancreatic cancer, metastatic cancer and the like. The best method for relieving the obstruction of the biliary tract is to arrange a biliary tract stent so that bile can flow to an intestinal cavity through the stent. In order to enhance the drainage effect, stents of various types and materials are continuously improved, and plastic stents, metal stents, drugs of various materials are obtained from stents with radioactive particles, biodegradable stents and the like.
In clinical practice, bacterial biofilms are found to cause restenosis of biliary stents, and bacterial infection is a key factor in bacterial biogenesis. In order to avoid biliary stent stenosis caused by bacterial infection, biliary stents coated with nano-silver coatings are often used in the prior art, which inhibit the formation of bacterial biofilms by slowly releasing silver ions, thereby prolonging the non-obstruction period after implantation of biliary stents. However, silver is not an essential trace element for human body, and the biliary tract stent coating prepared from pure silver has potential toxic and side effects on human health. In view of the above, how to ensure the excellent antibacterial performance of the surface coating of the biliary tract stent and eliminate the toxic and side effects thereof is a problem which needs to be solved urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a biliary tract stent surface nano coating which eliminates toxic and side effects brought by metal silver under the condition of considering the antibacterial performance of the nano silver coating.
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
and (3) taking the support material as a substrate, and preprocessing the substrate.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking the Ag-Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80-120sccm, substrate temperature of 100-120 ℃, sputtering pressure of 1.0-2.0Pa and sputtering power of 80-120W.
Putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.1-0.3mm is taken as hard particles in the treatment process, the gas pressure is 1.0-2.0MPa, the particle flow is 12-15g/s, the voltage is 15-20V, and the treatment time is 20-30 min.
Further, the bracket material is a plastic bracket or a metal bracket.
Further, the plastic support is polyethylene, polyurethane or polytetrafluoroethylene.
Further, the stent is an S-shaped stent, a double-layer stent or a Cotton-Leung stent.
Further, the pretreatment comprises pickling, oil removal, grinding, cleaning and drying, wherein a pickling solution is a 10% -25% HCl solution, grinding is performed by selecting 400#, 600#, 800# and 1200# abrasive paper respectively, oil removal is performed by selecting 10% -15% sodium carbonate solution, cleaning is performed by matching deionized water with ultrasonic auxiliary cleaning, and drying is performed under a protective atmosphere.
Further, the atomic content of Co in the composite target material is 25% -40%.
Preferably, the atomic content of Co in the composite target material is 29%.
The invention also provides a biliary tract stent surface nano-coating prepared by the method.
Cobalt is one of trace elements essential to human body, has no toxic side effect on human body, and has certain antibacterial property. In order to overcome the toxic and side effects of the nano-silver coating on the surface of the biliary tract stent, part of the metal element cobalt is selected to replace the metal element silver, and the safety of the biliary tract stent coating material is greatly improved at the cost of sacrificing the antibacterial performance of the part of the coating. Researches find that when the content of cobalt in the coating is 29%, the antibacterial performance and the toxic and side effects of the stent coating achieve the most excellent balance effect.
Detailed Description
The technical effects of the present invention are demonstrated below by specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-25at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gasThe flow rate was 80sccm, the substrate temperature was 120 ℃, the sputtering pressure was 1.0Pa, and the sputtering power was 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Example 2
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-29at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Example 3
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-35at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Example 4
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-40at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Comparative example 1
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-18at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Comparative example 2
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag-Co coating on the surface of the substrate by taking an Ag-50at% Co composite target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag-Co coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
Comparative example 3
A preparation method of a biliary tract stent surface nano coating comprises the following steps:
the method comprises the steps of using a metal material as a support substrate, pretreating the substrate, wherein the pretreatment comprises pickling, oil removal, polishing, cleaning and drying, the pickling solution is 15% of HCl solution, the polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, the oil removal is carried out by selecting 15% of sodium carbonate solution, the cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and the drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, and sputtering and depositing an Ag coating on the surface of the substrate by taking an Ag target as a sputtering source and argon as working gas. The background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, argon gas flow of 80sccm, substrate temperature of 120 ℃, sputtering pressure of 1.0Pa, and sputtering power of 120W.
And (2) putting the support substrate coated with the Ag coating into a supersonic particle bombardment device for surface nanocrystallization, wherein BN with the particle size of 0.3mm is taken as hard particles in the treatment process, the gas pressure is 2.0MPa, the particle flow is 12g/s, the voltage is 15V, and the treatment time is 30 min.
The antibacterial properties of examples 1 to 4 and comparative examples 1 to 3 were tested by the following methods: concentration of selected bacterial liquid is 5X 107The bacterial liquid for test (cfu/ml) of Staphylococcus aureus was added to the surface of the sample in an amount of 0.2ml, and the mixture was treated at 37 ℃ and RH>Culturing for 48h under 90% conditions, then taking out a sample, counting viable bacteria, and obtaining the antibacterial rate through counting. For each sample, 5 parallel runs were made, and the uncoated metal substrate holder was selected as a control. Wherein, the formula for calculating the antibacterial rate is as follows:
R(%)=(A-B)/A×100
in the formula: r represents the antibacterial rate;
a represents the average number of recovered bacteria in the control group;
b represents the average number of recovered bacteria of the samples of examples/comparative examples.
In order to objectively and fairly evaluate the antibacterial performance of each experimental sample, a bacterial liquid with an ultrahigh concentration is selected for testing, and the aim is to ensure that each sample cannot reach 100% of antibacterial rate. It should be noted that the antibacterial performance is measured by the antibacterial rate and the bacterial concentration, and the bacterial concentration adopted in the experiment cannot be achieved in the medical practice, that is, the antibacterial rate of the stent coating in the actual use process is higher than the following experimental data.
The antibacterial ratios of examples 1 to 4 and comparative examples 1 to 3 are shown in Table 1.
TABLE 1
Example 1 | Example 2 | Example 3 | Example 4 | Comparative example 1 | Comparative example 2 | Comparative example 3 | |
Antibacterial ratio/%) | 79.17 | 86.27 | 71.23 | 67.49 | 85.56 | 53.11 | 92.31 |
Further, the inventors studied the toxic and side effects of examples 1 to 4 and comparative examples 1 to 3, and the specific method was: the 7 groups of biliary coating stents were implanted in mice, in which the mice intestinal epithelial cells of comparative example 3 were found damaged (Ag accumulated at the cell damage) after 31 days, the mice intestinal epithelial cells of comparative example 1 were found damaged after 49 days, and the mice of examples 1 to 4 and comparative example 2 did not find damage of the intestinal epithelial cells at 80 days.
Claims (7)
1. A preparation method of a biliary tract stent surface nano coating comprises the following steps:
taking a biliary tract stent material as a substrate, and pretreating the substrate;
putting the dried substrate into a magnetron sputtering coating machine, taking an Ag-Co composite target material as a sputtering source, taking argon as working gas, and sputtering and depositing an Ag-Co coating on the surface of the substrate; the background vacuum degree is 5 multiplied by 10 during sputtering coating-5Pa, the flow rate of argon gas is 80-120sccm, the substrate temperature is 100-120 ℃, the sputtering pressure is 1.0-2.0Pa, the sputtering power is 80-120W, and the atomic content of Co in the composite target material is 25-40 percent;
the biliary tract stent substrate coated with the Ag-Co coating is put into a supersonic particle bombardment device for surface nano-treatment, BN with the particle size of 0.1-0.3mm is taken as hard particles in the treatment process, the gas pressure is 1.0-2.0MPa, the particle flow is 12-15g/s, the voltage is 15-20V, and the treatment time is 20-30 min.
2. A method of making according to claim 1, wherein: the bracket material is a plastic bracket or a metal bracket.
3. A method of manufacturing as claimed in claim 2, wherein: the plastic support is polyethylene, polyurethane or polytetrafluoroethylene.
4. A method of making according to claim 1, wherein: the biliary tract stent is an S-shaped stent, a double-layer stent or a Cotton-Leung stent.
5. The preparation method of claim 1, wherein the pretreatment comprises pickling, degreasing, polishing, cleaning and drying, wherein the pickling solution is 10% -25% HCl solution, the polishing is performed by 400#, 600#, 800# and 1200# sandpaper respectively, the degreasing is performed by 10% -15% sodium carbonate solution, the cleaning is performed by deionized water in cooperation with ultrasonic auxiliary cleaning, and the drying is performed in protective atmosphere.
6. The method according to any one of claims 1 to 5, wherein the atomic content of Co in the composite target material is 29%.
7. A nano-coating on the surface of a biliary tract stent, wherein the nano-coating is prepared by the method of any one of claims 1 to 6.
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