WO2021066667A1 - Procédé d'application d'un revêtement ionique-plasmique sous vide d'oxynitrure de titane à la surface de stents intravasculaires - Google Patents

Procédé d'application d'un revêtement ionique-plasmique sous vide d'oxynitrure de titane à la surface de stents intravasculaires Download PDF

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WO2021066667A1
WO2021066667A1 PCT/RU2019/000694 RU2019000694W WO2021066667A1 WO 2021066667 A1 WO2021066667 A1 WO 2021066667A1 RU 2019000694 W RU2019000694 W RU 2019000694W WO 2021066667 A1 WO2021066667 A1 WO 2021066667A1
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titanium
coating
metal
layer
thickness
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PCT/RU2019/000694
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English (en)
Russian (ru)
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Олег Станиславович КУЗЬМИН
Дмитрий Анатольевич ПЛЕХАНОВ
Михаил Викторович ЯКОВЛЕВ
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Общество С Ограниченной Ответственностью "Научно-Производственное Предприятие "Вакуумные Ионно-Плазменные Технологии"
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Priority to PCT/RU2019/000694 priority Critical patent/WO2021066667A1/fr
Publication of WO2021066667A1 publication Critical patent/WO2021066667A1/fr

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/02—Prostheses implantable into the body
    • A61F2/04—Hollow or tubular parts of organs, e.g. bladders, tracheae, bronchi or bile ducts
    • A61F2/06—Blood vessels
    • A61F2/07—Stent-grafts
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F2/00—Filters implantable into blood vessels; Prostheses, i.e. artificial substitutes or replacements for parts of the body; Appliances for connecting them with the body; Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • A61F2/82—Devices providing patency to, or preventing collapsing of, tubular structures of the body, e.g. stents
    • 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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
    • A61L27/30—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
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/40—Composite materials, i.e. containing one material dispersed in a matrix of the same or different 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
    • C23C14/06—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
    • C23C14/22—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
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/54—Controlling or regulating the coating process

Definitions

  • the invention relates to the field of coating using vacuum ion-plasma spraying, in particular to the coating of titanium oxynitride on the surface of metal intravascular stents by magnetron sputtering, and can be used for the deposition of thin films of metals and their compounds in various fields of technology.
  • the method consists in regulating the reaction time of the reagent gas for growing the metal and transition oxynitride (M x (ON) y ) layer and includes the following steps:
  • a vacuum chamber for sputtering equipped with a holder for ceramic and / or flexible substrates and a planar target cathode made of metal, transition metal or transition metal alloy;
  • Argon is fed into the atomization chamber for ion bombardment, and nitrogen and oxygen form a reactive gas plasma generated by radio frequency, while the oxygen + nitrogen / argon flow rate ratio is at least 0.02, the oxygen / nitrogen flow rate ratio is at least 0.01, and the gas synchronization time (gas flow sequence control): argon, nitrogen and oxygen alternately or a mixture in a spray chamber for at least 1 s.
  • gas synchronization time gas flow sequence control
  • the disadvantages of this method are the planar geometry of the sputtered target, the low effective sputtering process with an HF discharge, the large values of the time constants for changing the composition of the gaseous medium, which limits the deposition rate and can lead to a layered structure of the grown coating.
  • the process is carried out in a high-vacuum unit with a cryogenic vacuum pump.
  • the titanium atoms used for deposition are obtained by sputtering an electrode from a high-purity metal (99.99%).
  • the synthesis of a coating of titanium nitride oxides is carried out from the products of HF plasma formed in a special configuration of the magnetic field at a low pressure of working gases: argon, oxygen, nitrogen.
  • Titanium oxynitride (T ⁇ -NO) is applied to both the external and internal surfaces of the stent using the patented Hexacath process, which ensures the presence of NO compounds on the surface.
  • the high hardness and absence of defects in the coating ensures successful direct stenting and protects the stent from damage by calcites.
  • the deposition process is controlled by external parameters: the flow rate of the working gases, the operating modes of the RF plasma and bias power supplies, the procedure time or similar values for other proposed film deposition technologies (arc evaporation, thermochemical deposition).
  • the stability of the HF sputtering mode, and hence the structure of the coating is largely determined by the presence of secondary factors, such as the amount of erosion of the electrodes, the degree of contamination of the chamber with spraying products, and the chemical state of the electrode surface.
  • the lack of feedback, fixing the parameters in the deposition zone, as well as diffusion thermal effects accompanying the methods of filtered arc evaporation or the thermochemical CVD process will lead to an uncontrolled change in the properties of the coating. This, first of all, affects the concentration and localization of NO compounds, which have a bioactive effect on the tissues of the body, and not the total content of oxygen and nitrogen in the surface layer.
  • the bioactivity of the coating is determined by the dispersion of the nanocrystalline structure, i.e. the surface area of the crystallites of the ceramic layer [V.F. Pichugin, A.A. Pustovalova, K.E. Evdokimov et al. Structural features and physicochemical properties of nitrogen-containing titanium dioxide films grown by reactive magnetron sputtering. Films and coatings-2019, St-Peterburg. 507-510].
  • the deposition technologies proposed in the EPO patent [EP 1674117 (A1) - 2006-06-28] do not allow controlling this process through physical parameters.
  • planar geometry of the process does not provide a film coverage of the surface of more than 75-80%.
  • the present invention seeks to overcome the aforementioned problems and overcome one or more of the discussed disadvantages.
  • the basis of the invention is the task of applying uniform coatings by the method of vacuum ion-plasma (magnetron) deposition with high adhesive strength and the ability to withstand high plastic deformations (up to 200%) on such products, for example, as intravascular stents.
  • vacuum ion-plasma magnetic
  • plastic deformations up to 200%
  • the technical result is to obtain long-lasting titanium oxynitride coatings on metal intravascular stents, which combine the properties of bioinert titanium oxide and bioactive nitric oxide.
  • intravascular stents coated with the proposed method should provide an improved effect of artificial materials (titanium oxide-based coatings doped with nitrogen) on their thromboresistance by ensuring uniformity of functional properties, including the inner surface of stents, high deformation properties of the coating during stenting. products.
  • the problem is solved by the fact that the proposed method of applying a vacuum ion-plasma coating of titanium oxynitride (Ti-0-N) on the surface of metal intravascular stents (products) includes:
  • the electrodes of which have a cylindrical shape, in which:
  • a gradient transition layer from metal to titanium dioxide is formed with a thickness of 5-15 nm, preferably 10 ⁇ 2 nm,
  • the preliminary ion-plasma treatment of articles (stents) with a gas plasma generator is carried out at a pressure of 0.4-0.8 Pa, preferably 0.6 Pa, a discharge current of 5-10 A, preferably 7 A, and a pulse bias potential at the working table with parameters: pulse duration 3-25 ⁇ s with an amplitude of 500-700 V and a frequency of 10-80 kHz.
  • preliminary training of the dual magnetron sputtering system is carried out at an argon pressure of 0.07-0.15 Pa, a magnetron discharge power of 1.5-2.5 kW for 2-4 minutes.
  • the surface of the cathodes of the dual magnetron sputtering system (DMS) is cleaned; coating of open surfaces inside the working chamber with titanium metal; the residual pressure is reduced due to heterogeneous absorption by sputtered titanium, which ensures the absence of impurities and the ductility of the subsequently deposited metal layer on the products.
  • the deposition of the coating is carried out in the internal volume of the dual magnetron sputtering system formed by two cylindrical electrodes, with the planetary rotation of the products and supplying them with a pulse bias potential of 100-300 V with a frequency twice the frequency of the power supply pulses of the dual magnetron sputtering system, and pulse synchronization with polarity reversal on the electrodes.
  • the deposition of a metal adhesive sublayer (deposition of a titanium film) is carried out in an argon atmosphere at a pressure of 0.10-0.15 for 3-7 minutes;
  • the formation of an intermediate gradient transition layer from metal to titanium dioxide is carried out at a magnetron discharge power of 1.0-1.5 kW, while the oxygen consumption is selected in such a way that the beginning of the formation of amorphous titanium dioxide on the surface of the products occurs within 3-4 minutes, (accompanied, as a rule, by an increase in the total gas pressure from 0.10 Pa to 0.20 Pa);
  • the deposition of a functional oxynitride layer is carried out in an argon, oxygen and nitrogen atmosphere at a ratio of nitrogen and oxygen consumption from 0.5 to 2.5, a total pressure of 0.17 0.25 Pa and a discharge power of 3.0 3.5 kW at a frequency power supply 10 - 40 kHz.
  • the spectral characteristics of the radiation of the cathode plasma of the dual magnetron sputtering system are monitored and the flow rate of the gas components is adjusted in order to maintain the ratio integrated radiation intensity of titanium to oxygen, in order to stabilize the deposition parameters of a functional oxynitride coating
  • the control signal of the spectrometer is used, the optical axis of the recorded radiation of which is located in the cathode region parallel to the cylindrical surface of the electrodes.
  • the automatic control system regulates the oxygen consumption and, proportionally, the nitrogen consumption in order to stabilize the given relative intensity of the radiation of oxygen atoms of the plasma to the emission line of titanium atoms at a stabilized discharge power.
  • FIG. 1 shows a block diagram of the installation of vacuum ion-plasma deposition of coatings
  • FIG. 2 shows a block diagram of the N-T1O2 coating on a metal stent
  • Fig. 3 shows a data exchange diagram for the entire software package of the installation.
  • - in Fig. 4 shows a PEM image of the stent surface after testing in the zone of maximum plastic flow.
  • the installation (Fig. 1) contains a vacuum chamber 1 with a dual magnetron sputtering system (MS) 2 located in it with titanium cylindrical cathodes 3 to which a lock chamber 6 is connected through a gate 5 with a gas plasma generator 7 installed in it for preliminary ion-plasma treatment and a transport planetary work table 8 for loading products; high-vacuum pumping system including oil-free pumping means; three-channel gas supply system 11; a power supply for the magnetron sputtering system 12, a power supply for the bias potential of the working table 13, power supplies for the gas discharge 14, 15 of the plasma generator 7; an automatic control system 16 and means for monitoring the technological process, including a spectrometric analyzer of plasma radiation 17, pressure and cooling sensors, and a control computer 18.
  • the electromechanical drive M provides a linear movement of the working table 8 into the vacuum chamber 1 using a telescopic screw device 21.
  • the working table 8 is equipped with planetary satellites and has attachments for the workpieces.
  • Vacuum chamber 1 is a sealed vacuum volume, inside of which there is a dual magnetron system 2 with a working area for processing along the axis of cylindrical titanium electrodes (cathodes) 3.
  • the vacuum chamber 1 has an optical channel for transmitting the radiation of the magnetron discharge to the automatic spectrometer 17.
  • the optical axis of the probe 27 is parallel to the surface of the cylindrical cathodes 3 in the area of the near-cathode plasma.
  • an AvaSpec-Mini 4096CL-UV-5 spectrometer can be used as a spectrometer
  • an FC-UVIR600-2-ME fiber optic cable can be used as a probe.
  • the MS magnetron sputtering system consists of two, one above the other, identical cylindrical magnetron electrodes (or electrode devices) 2 with their own magnetic systems.
  • the control and monitoring system 16 is designed to control the units and mechanisms of the installation in accordance with the specified algorithms for conducting the technological process.
  • the products after ion treatment in the lock chamber 6, are moved into the vacuum chamber 1 by a telescopic transport system (telescopic screw device 21) of the working table 8, and during the spraying of coatings, a circular planetary motion of the processed products is carried out.
  • a telescopic transport system telescopic screw device 21
  • Symmetrical bipolar power from the power supply 12 is fed to magnetron electrodes 2, deposition is accompanied by a pulsed bias potential on the products, synchronized with the polarity change on the electrodes 3.
  • the stability of the film synthesis process is ensured by monitoring the intensity of the spectral lines of radiation of titanium, nitrogen and oxygen atoms in the magnetron discharge plasma, moreover, the control signal to the regulators of the oxygen and nitrogen gas consumption is normalized to the intensity of the titanium emission line, and the power of the magnetron discharge and the argon consumption are stabilized.
  • the structural diagram of the applied coatings is shown in figure 2, where 1 is the stent material, 2 is the titanium sublayer, 3 is a transition gradient layer, 4 is a functional layer of titanium oxynitride.
  • Example 1 Deposition of the surface layer at a ratio of consumption of gas reagents N2 / O2 equal to 1.5 (with the parameters indicated in Table 1).
  • Loading of products - pre-defatted metal stents (20 metal cardiostents 1.6x18 mm manufactured by "Balton” Ltd.) - is carried out by suspension on the planetary satellites of the desktop 8 of the vacuum ion-plasma installation (Fig. 1) by a method that minimizes the contact area with samples.
  • Samples-witnesses (2 pcs. - glass, 2 pcs. - steel 316L (AISI) are placed in identical positions. Loops of a silver-plated copper conductor MC16-13 0.02 wire were used as a material for suspension. Diameter 45 microns provides a small contact area with the sample and has sufficient rigidity for fixation. Processing of products in a vacuum ion-plasma installation.
  • the working gas is supplied to the plasma generator - argon (position No. 2: 1.08 ⁇ 0.05 l / h (30% of the maximum range of 3.6 l / h)); the drive of the working table is switched on in reverse mode (position N ° 3: M - out); processing parameters are set and switched on (positions N ° 4-9): cathode heating (PS1 40 A, on) and generator discharge power (PS2 7.5A, on); Bias voltage pulses are applied to the desktop (PS3 600 V, 6 ⁇ s, 40 kHz, on); the timer for the operation is started (position ° 10: Pause 300 s). At the end of the timer, the power supply from the plasma generator is turned off (position N ° 10: PS1 off, position Nell: PS2 off) and reverse is turned off (position N ”12: M - off).
  • DMS dual magnetron sputtering system
  • the program corrects the flow of the working gas-argon into the working chamber (position N ° 14: VF1 - 12%); the bipolar power supply is switched on to the DMS electrodes in the specified mode (positions N ° 15-16: PS4 - 2.0 kW, 10 kHz, on); the magnetron is trained for the time specified by the program parameter (position N ° 17: PAUSE 180 s), after which the discharge voltage is removed (position N ° 18: PS4 - off).
  • the drive of the desktop is switched on in the direction of transportation from the lock (position Nel9: M - in); the bias potential is reduced to values suitable for deposition of coatings (position N ° 20: PS3 250 V, 20 kHz); the operation of the inductive position sensor in the working chamber is expected, after which the next operation starts.
  • a metal adhesive sublayer (position 2 in figure 2).
  • the trained LCA is switched on in the metal deposition mode (position 1 21: VF1 - 6.5 N ° 22: PS4 - on) and the titanium film is deposited within the time specified by the program (position N ° 24: PAUSE - 300 s) , which determines the thickness of the metal sublayer 30 ⁇ 5 nm.
  • Products installed on the working table make planetary motion in the working area of the LCA.
  • the discharge power is reduced (position N ° 25: PS4 - 1.0 kW, 80 kHz) and the oxygen supply (position N ° 26: VF2 - 12%) is switched on at a given flow rate, which ensures a smooth transition to the oxide deposition mode within 3-4 minutes ...
  • the spread in the formation time of the required parameters, and hence the thickness of the transition layer, depends on various secondary factors, therefore the operation timer is set deliberately exceeding the maximum required procedure time (position N ° 27: Pause 240 s).
  • a gradient layer (position 3 in Fig. 2) is formed from titanium metal to amorphous dioxide with a thickness of about 10 ⁇ 2 nm.
  • oxygen consumption correction position N ° 28: VF2 - 3.40%
  • inclusion of leakage into the nitrogen chamber position N ° 29: VF3 - 5.10%) in accordance with the preset starting values (VF2, VF3)
  • output of LCA parameters to a given discharge power position 30: PS4 - 3.0 kW
  • position I Pause - 30 s
  • the processed control signal of the spectrometer is used to correct oxygen and nitrogen in order to stabilize the deposition parameters of the functional coating.
  • the software (software) of the spectrometer is an integral part of the software of the installation.
  • Simle-Scada is an OPC client that connects to the OPC server.
  • FIG. 3 shows a data exchange diagram of the entire software package. Functionally, the spectrometer software can be divided into three modules:
  • the data processing program interacts with the spectrometer through the AvaSpec DLL, processes the received data in accordance with the radiation peak integration algorithm, and interacts with the OPC server to receive commands and issue the calculation results.
  • the OPC server exchanges data with the Simple-Scada system of the plant control program.
  • the OPC server interface includes a set of variables with fixed names and data types.
  • the control signal implements the following function of the measured spectrum of the DMS plasma: where Ii is the integrated intensity of the signal from the ROM of the matrix spectrometer corresponding to the peak of the radiation wavelength of titanium atoms T ⁇ h, and g I * ⁇ corresponds to the emission of molecular oxygen.
  • Ii is the integrated intensity of the signal from the ROM of the matrix spectrometer corresponding to the peak of the radiation wavelength of titanium atoms T ⁇ h
  • g I * ⁇ corresponds to the emission of molecular oxygen.
  • the system maintains a constant ratio of the radiation peaks of the plasma components at a stabilized discharge power.
  • a predetermined time interval position N ° 33: Pause 1800 s
  • the power supply to the magnetron is turned off, the potential is removed from the working table, the supply of working gases to the vacuum system is shut off (positions N «34 - Ke41).
  • the deposition of a layer of N-T1O2 position 4 in Fig. 2) with a thickness of 160 ⁇ 15 nm occurs.
  • the unit is ready for the next machining cycle.
  • the given technological program corresponds to the mode of deposition of the surface layer with the ratio of the consumption of gas reagents N2 / O2 equal to 1.5, set by the regulators VF2, VF3 (Fig. 1) at the program step 28, 29.
  • the mechanical properties of the coatings were investigated by the method of dynamic nanoindentation using an NHT-S-000X device at a load of 5 mN, as well as using a NanoScan scanning nanohardness tester. Nanohardness, Young's modulus, and contact stiffness were determined by the Oliver-Pharr method. Elastic recovery was determined from load-unload curves.
  • Tests for plastic deformation of the treated stents were carried out by the method of balloon expansion to the maximum diameter at a test pressure in the standard system up to 2.0 MPa, followed by electron microscopy of the zones of tension and compression.
  • the thickness of the Ti – O – N coating was determined by the method of optical ellipsometry of flat witness specimens treated simultaneously with stents.
  • the spectroanalytical complex "SAG-1891" was used. The calculation was carried out using the Cauchy dispersion equation for transparent or semitransparent films.
  • the morphological properties of the surface of the samples were analyzed before and after exposure using a scanning microscope (XL 30 ESEM-FEG Philips, voltage 3.0 kV). Elemental and chemical analysis - using EDS and FTIR microscopy.
  • the hydrophilicity / hydrophobicity of the coating surface was determined by measuring the contact angles using an OSA 20 instrument (DataPhysics Instrument Gmbh) with the appropriate SCA 202 software.
  • MMSC human mesenchymal stem cells
  • T1O2 consist of an amorphous phase with the presence of anatase and rutile nanocrystallites.
  • CSR coherent scattering regions
  • XPS HR high-resolution X-ray photoelectron spectroscopy
  • Nitrogen-containing N-T1O 2 films deposited by reactive magnetron sputtering have high values of nanohardness (up to 28 GPa), Young's modulus (up to 231 GPa), elastic recovery (up to 70%), and high adhesive strength (up to 376 MPa), and this determines good elastic properties and crack resistance.
  • the deformation of the stents by the test pressure showed that the process occurs without cracking and detachment.
  • Figure 4 shows a PEM image of the surface after testing in the zone of maximum plastic flow, where a is an uncoated stent; b - stent coated with Ti + N-T1O 2 (example) after balloon deformation of 2.0 MPa.
  • Ti + N-T1O 2 does not cause differentiation of the culture into osteoblasts, cartilage cells and fat cells.
  • s_napyleniem Ti + N-T1O 2 significantly reduced (by 40%, p ⁇ 0.05) mean number MMSC (due to migration and cell division) in comparison with the coated hm 2.
  • the proposed method provides the application of uniform nanocomposite multicomponent (Ti-0-N) coatings on vascular stents, due to the uniform deposition of the material in argon and reaction gases: oxygen, nitrogen.
  • the effectiveness of the method is achieved by sluicing products, dividing the zones of ion-plasma cleaning of the surface of products and spraying, moving the working table for transporting products from the sluice to the working chamber with their planetary rotation inside a special cylindrical dual magnetron system in combination with synchronized pulse modes of supply of the displacement potential of the working table, control of the deposition process based on the spectral characteristics of the plasma, the use of modern vacuum equipment and controls, automation of the technological process.

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Abstract

L'invention se rapporte au domaine de l'application de revêtements en utilisant la pulvérisation ionique-plasmique sous vide, et notamment l'application de revêtements d'oxynitrure de titane sur la surface de stents intravasculaires métalliques selon un procédé de pulvérisation par magnétron, et peut être utilisée pour appliquer des films fins de métaux et de leurs composés dans divers domaines des techniques. En termes de propriétés, les stents intravasculaires sur lesquels un revêtement est appliqué selon ce procédé, doivent assurer une meilleure influence des matériaux artificiels (revêtements base d'oxyde de titane dopés par de l'azote) sur leur thromborésistance, ceci en assurant l'uniformité des propriétés fonctionnelles, y compris la surface interne des stents, des propriétés de déformation élevées du revêtement lors de pose du stent sur le site. L'article obtenu selon ce procédé (stent métallique intravasculaire avec revêtement) comprend un revêtement comprenant une couche interne métallique en titane de grande pureté d'une épaisseur de 15-40 nm, une couche de transition à gradient depuis le métal vers le dioxyde de titane d'une épaisseur de 5 - 15 nm, et une couche supérieure fonctionnelle d'un revêtement d'oxynitrure d'une épaisseur de 100 - 200 nm.
PCT/RU2019/000694 2019-09-30 2019-09-30 Procédé d'application d'un revêtement ionique-plasmique sous vide d'oxynitrure de titane à la surface de stents intravasculaires WO2021066667A1 (fr)

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PCT/RU2019/000694 WO2021066667A1 (fr) 2019-09-30 2019-09-30 Procédé d'application d'un revêtement ionique-plasmique sous vide d'oxynitrure de titane à la surface de stents intravasculaires

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PCT/RU2019/000694 WO2021066667A1 (fr) 2019-09-30 2019-09-30 Procédé d'application d'un revêtement ionique-plasmique sous vide d'oxynitrure de titane à la surface de stents intravasculaires

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8372250B2 (en) * 2007-07-23 2013-02-12 National Science And Technology Development Agency Gas-timing method for depositing oxynitride films by reactive R.F. magnetron sputtering
EA022113B1 (ru) * 2010-02-26 2015-11-30 Имк Текнолоджи Консалтантс Гмбх Защитные покрытия для медицинских имплантатов
WO2019164422A1 (fr) * 2018-02-25 2019-08-29 Общество С Ограниченной Ответственностью "Научно-Производственное Предприятие "Вакуумные Ионно-Плазменные Технологии" Installation ionique-plasmique sous vide pour appliquer un revêtement d'oxynitrure de titane à la surface de stents métalliques intravasculaires

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8372250B2 (en) * 2007-07-23 2013-02-12 National Science And Technology Development Agency Gas-timing method for depositing oxynitride films by reactive R.F. magnetron sputtering
EA022113B1 (ru) * 2010-02-26 2015-11-30 Имк Текнолоджи Консалтантс Гмбх Защитные покрытия для медицинских имплантатов
WO2019164422A1 (fr) * 2018-02-25 2019-08-29 Общество С Ограниченной Ответственностью "Научно-Производственное Предприятие "Вакуумные Ионно-Плазменные Технологии" Installation ionique-plasmique sous vide pour appliquer un revêtement d'oxynitrure de titane à la surface de stents métalliques intravasculaires

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