CN113025984A - Modification method of surface ZrC coating of intravascular stent - Google Patents
Modification method of surface ZrC coating of intravascular stent Download PDFInfo
- Publication number
- CN113025984A CN113025984A CN202110559575.7A CN202110559575A CN113025984A CN 113025984 A CN113025984 A CN 113025984A CN 202110559575 A CN202110559575 A CN 202110559575A CN 113025984 A CN113025984 A CN 113025984A
- Authority
- CN
- China
- Prior art keywords
- substrate
- coating
- gas
- nitriding
- zrc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 52
- 239000011248 coating agent Substances 0.000 title claims abstract description 51
- 238000002715 modification method Methods 0.000 title description 4
- 238000005121 nitriding Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 210000004204 blood vessel Anatomy 0.000 claims abstract description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 48
- 239000000758 substrate Substances 0.000 claims description 46
- 238000000137 annealing Methods 0.000 claims description 33
- 229910052786 argon Inorganic materials 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 24
- 238000004544 sputter deposition Methods 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000005554 pickling Methods 0.000 claims description 16
- 238000005498 polishing Methods 0.000 claims description 16
- 239000010935 stainless steel Substances 0.000 claims description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 14
- 230000002792 vascular Effects 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000012495 reaction gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 claims description 3
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 3
- 229910001285 shape-memory alloy Inorganic materials 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 238000005260 corrosion Methods 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 8
- 238000005530 etching Methods 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 239000002344 surface layer Substances 0.000 abstract description 2
- 229910052726 zirconium Inorganic materials 0.000 abstract description 2
- 238000007781 pre-processing Methods 0.000 description 12
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 210000000709 aorta Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 230000002490 cerebral effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 210000005259 peripheral blood Anatomy 0.000 description 1
- 239000011886 peripheral blood Substances 0.000 description 1
- 239000012890 simulated body fluid Substances 0.000 description 1
- 230000002966 stenotic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- A61L31/02—Inorganic 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
- A61L31/08—Materials for coatings
-
- 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
-
- 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
-
- 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
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
-
- 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
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
- C23C8/38—Treatment of ferrous surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Surgery (AREA)
- Public Health (AREA)
- Vascular Medicine (AREA)
- Animal Behavior & Ethology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Epidemiology (AREA)
- Inorganic Chemistry (AREA)
- Media Introduction/Drainage Providing Device (AREA)
- Physical Vapour Deposition (AREA)
- Materials For Medical Uses (AREA)
Abstract
A method for modifying ZrC coating on surface of blood vessel support features that ion nitriding is used to introduce N element to existing ZrC coating for obtaining a medical coating containing Zr, C and N elements on surface layer, and the existing self-corrosion current density can be increasedAbout 2-5. mu.A/cm2The self-corrosion current density of the ZrC coating is reduced to 1.5 mu A/cm2The following, and, in a highly preferred embodiment, the self-etching current density can be reduced even to 0.759. mu.A/cm2The corrosion resistance of the ZrC coating of the conventional intravascular stent is greatly improved.
Description
Technical Field
The invention relates to a modification method of a ZrC coating, in particular to an ion nitriding modification method of a ZrC coating on the surface of a vascular stent.
Background
The blood vessel stent is characterized in that an inner stent is placed in a diseased blood vessel section to achieve the purposes of supporting a blood vessel at a stenotic occlusion section, reducing the elastic retraction and the plasticity of the blood vessel and keeping the blood flow of a lumen, and according to the using parts of the stent, the blood vessel stent is mainly a coronary stent, a peripheral blood vessel stent, an aorta blood vessel stent, a cerebral blood vessel stent and the like. Metal materials (medical stainless steel, nickel-titanium memory alloy and the like) are widely applied to the field of intravascular stents, but the corrosion resistance of a bare metal stent cannot meet the complicated liquid environment of a human body generally, so that the corrosion resistance of the metal stent material is improved by adopting a surface coating mode in the prior art, wherein a ZrC coating is one of a plurality of stent coatings. However, the self-corrosion current of the ZrC coating of the prior vascular stent is about 2-5 muA/cm2This corrosion resistance has yet to be improved.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for modifying a ZrC coating on the surface of a vascular stent, which improves the corrosion resistance of the ZrC coating by an ion nitriding process.
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the following steps of taking a blood vessel stent material as a substrate, pretreating the substrate, wherein the pretreatment comprises pickling, polishing, cleaning and drying, the pickling selects 10-20% HCl solution, the polishing selects 400#, 600#, 800# and 1200# abrasive paper respectively, the cleaning selects deionized water to cooperate with ultrasonic auxiliary cleaning, and the drying is carried out in protective atmosphere;
putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate;
taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 1 multiplied by 10-5Pa-5×10-5Pa, argon flow 50-70sccm, liningThe bottom temperature is 180 ℃ and 250 ℃, the sputtering pressure is 3.0-8Pa, and the sputtering power is 80-120W;
the vascular stent coated with the ZrC coating is placed into an ion nitriding furnace, the background vacuum degree is 5-10Pa, the workpiece nitriding temperature is 600-750 ℃, the heating rate is 15-25 ℃/min, and the current density is 3.0-5.0mA/cm2The working voltage is 630-760V, the working pressure is 500-800Pa, the distance between the anode and the cathode is 40-55mm, and the nitriding time is 8-10 h;
taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress annealing under inert gas, wherein the annealing temperature is 300-400 ℃, and the annealing time is 1.5-2.0 h.
Further, the stent material is medical stainless steel or nickel titanium memory alloy.
Further, the medical stainless steel is 316L stainless steel.
Further, the reaction gas for ion nitriding is ammonia gas.
Further, the reaction gas for ion nitriding is a mixed gas of nitrogen and hydrogen.
Preferably, the nitrogen in the mixed gas accounts for 25% -75%.
More preferably, the nitrogen in the mixed gas accounts for 62%.
Introducing element N into the existing ZrC coating by ion nitriding to obtain a medical material coating containing three elements of Zr, C and N on the surface layer, wherein the method can lead the existing self-corrosion current density to be about 2-5 mu A/cm2The self-corrosion current density of the ZrC coating is reduced to 1.5 mu A/cm2The following, and, in a highly preferred embodiment, the self-etching current density can be reduced even to 0.759. mu.A/cm2The corrosion resistance of the ZrC coating of the conventional intravascular stent is greatly improved.
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 method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 5 multiplied by 10-5Pa, the flow rate of argon gas of 50sccm, the substrate temperature of 180 ℃, the sputtering pressure of 3.0Pa and the sputtering power of 80W.
Putting the vascular stent covered with the ZrC coating into an ion nitriding furnace, performing ion nitriding by taking ammonia gas as reaction gas, wherein the background vacuum degree is 10Pa, the nitriding temperature of a workpiece is 600 ℃, the heating rate is 15 ℃/min, and the current density is 3.0mA/cm2The working voltage is 760V, the working pressure is 500Pa, the distance between the anode and the cathode is 40mm, and the nitriding time is 8 h.
And taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
Example 2
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source, taking argon as working gas, and placing the target on a support substrateDepositing ZrC coating on the surface, wherein the background vacuum degree is 5 multiplied by 10-5Pa, the flow rate of argon gas of 50sccm, the substrate temperature of 180 ℃, the sputtering pressure of 3.0Pa and the sputtering power of 80W.
The vascular stent coated with the ZrC coating is put into an ion nitriding furnace and mixed gas of nitrogen and hydrogen (50% N)2+50%H2) Performing ion nitriding for reaction gas, wherein the background vacuum degree is 10Pa, the nitriding temperature of the workpiece is 600 ℃, the temperature rise rate is 15 ℃/min, and the current density is 3.0mA/cm2The working voltage is 760V, the working pressure is 500Pa, the distance between the anode and the cathode is 40mm, and the nitriding time is 8 h.
And taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
Example 3
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 5 multiplied by 10-5Pa, the flow rate of argon gas of 50sccm, the substrate temperature of 180 ℃, the sputtering pressure of 3.0Pa and the sputtering power of 80W.
The ZrC coated vascular stent is put into an ion nitriding furnace and thermally decomposed by ammonia gas (25% N)2+75%H2) Performing ion nitriding for reaction gas, wherein the background vacuum degree is 10Pa, the nitriding temperature of the workpiece is 600 ℃, the temperature rise rate is 15 ℃/min, and the current density is 3.0mA/cm2The working voltage is 760V, the working pressure is 500Pa, and the voltage of the anode and the cathode is twoThe distance is 40mm, and the nitriding time is 8 h.
And taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
Example 4
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 5 multiplied by 10-5Pa, the flow rate of argon gas of 50sccm, the substrate temperature of 180 ℃, the sputtering pressure of 3.0Pa and the sputtering power of 80W.
The vascular stent coated with the ZrC coating is put into an ion nitriding furnace and mixed gas of nitrogen and hydrogen (75% N)2+25%H2) Performing ion nitriding for reaction gas, wherein the background vacuum degree is 10Pa, the nitriding temperature of the workpiece is 600 ℃, the temperature rise rate is 15 ℃/min, and the current density is 3.0mA/cm2The working voltage is 760V, the working pressure is 500Pa, the distance between the anode and the cathode is 40mm, and the nitriding time is 8 h.
And taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
Example 5
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 5 multiplied by 10-5Pa, the flow rate of argon gas of 50sccm, the substrate temperature of 180 ℃, the sputtering pressure of 3.0Pa and the sputtering power of 80W.
The vascular stent coated with the ZrC coating is put into an ion nitriding furnace and mixed gas of nitrogen and hydrogen (62 percent N)2+38%H2) Performing ion nitriding for reaction gas, wherein the background vacuum degree is 10Pa, the nitriding temperature of the workpiece is 600 ℃, the temperature rise rate is 15 ℃/min, and the current density is 3.0mA/cm2The working voltage is 760V, the working pressure is 500Pa, the distance between the anode and the cathode is 40mm, and the nitriding time is 8 h.
And taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
Comparative example 1
A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the steps of taking medical 316L stainless steel as a support substrate, preprocessing the substrate, wherein the preprocessing comprises pickling, polishing, cleaning and drying, a pickling solution is a 10% HCl solution, polishing is respectively carried out by selecting 400#, 600#, 800# and 1200# abrasive paper, cleaning is carried out by matching deionized water with ultrasonic auxiliary cleaning, and drying is carried out under a protective atmosphere.
And putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate.
Taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 5 multiplied by 10-5Pa, argon flow of 50sccm, substrate temperature of 180 ℃,the sputtering pressure was 3.0Pa, and the sputtering power was 80W.
And taking out the work piece coated with the ZrC coating, putting the work piece into an annealing furnace, and performing stress relief annealing in inert gas, wherein the annealing temperature is 300 ℃, and the annealing time is 1.5 h.
The test samples of examples 1 to 5 (corresponding to A, B, C, D, E) and comparative example 1 (corresponding to M) were subjected to an electrochemical corrosion test in a simulated body fluid (PBS) to evaluate the corrosion resistance, and a blank control group (corresponding to N) of 316L stainless steel for medical use, which was not subjected to a coating treatment, was subjected to the same pretreatment and annealing treatment as those of the examples in order to ensure the accuracy of the test. The self-etching current densities of the respective test samples are shown in Table 1.
TABLE 1 self-Corrosion Current Density of the respective test samples
| Numbering | A | B | C | D | E | M | N |
| Self-corrosion current density mu A/cm2 | 1.453 | 1.421 | 1.572 | 1.013 | 0.759 | 2.167 | 4.209 |
As can be seen from Table 1, the corrosion resistance of the ZrC coated work piece was improved by the ion nitriding modification treatment, and when a specific nitriding process was selected (as in example 5), the resulting test specimen had a self-etching current density of only 0.759. mu.A/cm2And the medical practice use scene of the ZrC coating intravascular stent is greatly expanded.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for modifying a ZrC coating on the surface of an intravascular stent comprises the following steps:
the method comprises the following steps of taking a blood vessel stent material as a substrate, pretreating the substrate, wherein the pretreatment comprises pickling, polishing, cleaning and drying, the pickling selects 10-20% HCl solution, the polishing selects 400#, 600#, 800# and 1200# abrasive paper respectively, the cleaning selects deionized water to cooperate with ultrasonic auxiliary cleaning, and the drying is carried out in protective atmosphere;
putting the dried substrate into a magnetron sputtering coating machine, introducing argon, and carrying out plasma bombardment on the substrate;
taking a Zr-7.8wt% graphite composite target as a sputtering source and argon as working gas, and depositing a ZrC coating on the surface of the support substrate, wherein the background vacuum degree is 1 multiplied by 10-5Pa-5×10-5Pa, argon flow of 50-70sccm, substrate temperature of 180-250 ℃, sputtering pressure of 3.0-8Pa and sputtering power of 80-120W;
the vascular stent coated with the ZrC coating is put into an ion nitriding furnace and is nitridedIn the process, the background vacuum degree is 5-10Pa, the workpiece nitriding temperature is 600-750 ℃, the temperature rise rate is 15-25 ℃/min, and the current density is 3.0-5.0mA/cm2The working voltage is 630-760V, the working pressure is 500-800Pa, the distance between the anode and the cathode is 40-55mm, and the nitriding time is 8-10 h;
taking out the workpiece subjected to ion nitriding, putting the workpiece into an annealing furnace, and performing stress annealing under inert gas, wherein the annealing temperature is 300-400 ℃, and the annealing time is 1.5-2.0 h.
2. A method as claimed in claim 1, characterized by: the stent is made of medical stainless steel or nickel-titanium memory alloy.
3. A method as claimed in claim 2, characterized in that: the medical stainless steel is 316L stainless steel.
4. The method of claim 1, wherein the reactive gas for ion nitriding is ammonia.
5. The method according to claim 1, wherein the reaction gas for ion nitriding is a mixed gas of nitrogen and hydrogen.
6. The method of claim 5, wherein the nitrogen gas is present in the mixed gas in a proportion of 25% to 75%.
7. The method of claim 5, wherein the mixed gas contains nitrogen at a ratio of 62%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110559575.7A CN113025984B (en) | 2021-05-21 | 2021-05-21 | Modification method of surface ZrC coating of intravascular stent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110559575.7A CN113025984B (en) | 2021-05-21 | 2021-05-21 | Modification method of surface ZrC coating of intravascular stent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113025984A true CN113025984A (en) | 2021-06-25 |
| CN113025984B CN113025984B (en) | 2021-08-06 |
Family
ID=76455500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110559575.7A Expired - Fee Related CN113025984B (en) | 2021-05-21 | 2021-05-21 | Modification method of surface ZrC coating of intravascular stent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113025984B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808595A (en) * | 2007-06-11 | 2010-08-18 | 史密夫和内修有限公司 | Ceramic layered medical implant |
| CN105695801A (en) * | 2016-03-02 | 2016-06-22 | 戴俊杰 | Medical surgical blade |
| CN105734327A (en) * | 2016-03-19 | 2016-07-06 | 蔡建斌 | Drill bit for orthopedic operation |
| CN108129167A (en) * | 2018-01-09 | 2018-06-08 | 中南大学 | A kind of high temperature resistant anti-yaw damper is modified ZrC-SiC ceramic coatings and preparation method |
-
2021
- 2021-05-21 CN CN202110559575.7A patent/CN113025984B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808595A (en) * | 2007-06-11 | 2010-08-18 | 史密夫和内修有限公司 | Ceramic layered medical implant |
| CN105695801A (en) * | 2016-03-02 | 2016-06-22 | 戴俊杰 | Medical surgical blade |
| CN105734327A (en) * | 2016-03-19 | 2016-07-06 | 蔡建斌 | Drill bit for orthopedic operation |
| CN108129167A (en) * | 2018-01-09 | 2018-06-08 | 中南大学 | A kind of high temperature resistant anti-yaw damper is modified ZrC-SiC ceramic coatings and preparation method |
Non-Patent Citations (1)
| Title |
|---|
| L. WANG ET AL.: ""Surface modification of biomedical AISI 316L stainless steel with zirconium carbonitride coatings"", 《APPLIED SURFACE SCIENCE》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113025984B (en) | 2021-08-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2262919B1 (en) | Treatment of metal components | |
| US6617057B2 (en) | Composite vapor deposited coatings and process therefor | |
| US4981756A (en) | Method for coated surgical instruments and tools | |
| US6447664B1 (en) | Methods for coating metallic articles | |
| CN113025984B (en) | Modification method of surface ZrC coating of intravascular stent | |
| CN101988182A (en) | Surface modification method for wear-resisting orthodontic arch wire and obtained wear-resisting arch wire | |
| US4999259A (en) | Chrome-coated stainless steel having good atmospheric corrosion resistance | |
| WO2021218089A1 (en) | High-nitrogen nickel-free austenitic stainless steel seamless thin-walled tube | |
| CN114377198B (en) | Biodegradable magnesium-based material containing degradable film layer and preparation method and application thereof | |
| CN101507836B (en) | Thermal processing method capable of increasing medical titanium implant surface performance | |
| CN114481074B (en) | Magnesium alloy surface coating material and application thereof | |
| CN114369807B (en) | Oral arch wire and preparation method thereof | |
| CN211460696U (en) | Novel blood vessel support | |
| CN111020475A (en) | Novel AT coating | |
| CN108048892A (en) | A kind of Antibacterial using magnesium/magnesium alloy as matrix is surface-treated preparation method | |
| CN111840659B (en) | High-safety blood vessel support without nickel metal medicine elution and its making method | |
| CN112301395B (en) | Preparation method of nickel-titanium alloy attached with ceramic and polymer composite membrane | |
| CN109423605A (en) | Titanium doped non-hydrogen diamond membrane, preparation method and applications | |
| RU2156831C1 (en) | Method of improving corrosion resistance of steel-based cutting tools | |
| CN115142026B (en) | Method for obtaining compact calcium-phosphorus coating on magnesium alloy surface | |
| CN114381642B (en) | Magnesium implant biomedical material containing surface passivation layer and manufacturing method thereof | |
| CN113564550A (en) | High-hardness corrosion-resistant zirconium nitride coating and preparation method thereof | |
| DE10044559A1 (en) | Coated implant | |
| Dumbleton et al. | Coating and surface modification | |
| CN111850668A (en) | Surface finishing method for small-caliber pipe net-shaped metal sample |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210806 |