CN110129748A - The preparation method of cardiac vascular medical equipment surfaces Ti-Cu-N coating with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood - Google Patents

The preparation method of cardiac vascular medical equipment surfaces Ti-Cu-N coating with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood Download PDF

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CN110129748A
CN110129748A CN201910393873.6A CN201910393873A CN110129748A CN 110129748 A CN110129748 A CN 110129748A CN 201910393873 A CN201910393873 A CN 201910393873A CN 110129748 A CN110129748 A CN 110129748A
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target
coating
sputtering
argon gas
preparation
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景凤娟
黄斌
邓乔元
任倩
覃利娜
谢东
冷永祥
黄楠
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Southwest Jiaotong University
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Southwest Jiaotong University
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    • A—HUMAN NECESSITIES
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    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/28—Materials for coating prostheses
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    • A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • 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
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    • 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
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    • 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
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
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    • 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
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    • C23C14/0641—Nitrides
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C23C14/32—Vacuum evaporation by explosion; by evaporation and subsequent ionisation of the vapours, e.g. ion-plating
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    • A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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Abstract

The preparation method of the invention discloses a kind of cardiac vascular medical equipment surfaces Ti-Cu-N coating with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood；The doping of Cu is 4-50at% in coating, with a thickness of 0.02 micron；Ti-Cu-N coating is prepared in cardiac vascular medical equipment surfaces using the method for forming Cu, Ti, N ion and atom in a vacuum, cardiac vascular medical instrument is metal and one of alloy or high polymer；Magnetically controlled sputter method prepares coating can be used, sputtering target material is one of Ti-Cu mosaic target, Ti and the bis- targets of Cu, Ti-Cu alloys target.It can also be one of Ti-Cu mosaic target, Ti-Cu alloys target using the method prepares coating of metallic cathode arc source deposition, metallic cathode target.Ti-Cu-N coating release Cu ion prepared by the present invention and catalysis release NO, have the function of antibacterial, anticoagulation and anti-proliferation of smooth muscle；Bacterium infection, thrombosis, restenosis hyperplasia after can solving the problems, such as medical instrument and artificial organs implantation for cardiac vascular medical instrument.

Description

Cardiac vascular medical equipment surfaces Ti-Cu- with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood The preparation method of N coating
Technical field
The present invention relates to biomedical material technologies, and in particular to a kind of for cardiac vascular medical equipment surfaces Ti-Cu-N coating, preparation method and applications.
Background technique
The materials such as 316L stainless steel, medical cobalt alloy, ultra-high molecular weight polyethylene, terylene have preferable mechanical property and Biocompatibility is usually used in preparing the medical instrument and artificial organs of the implantable such as intravascular stent, heart valve, artificial blood pump； However, these implantation materials easily caused in patient bacterium infection [Huang Yunchao, Yang Kaiyun, Lei Yujie, Zhao Guangqiang, Li Xiaoming, Gao Jia, artificial valve material bacteria stick the relationship with bacterial growth, Chinese Tissue Engineering Study and clinical rehabilitation, and 2008,12 (39), 7777], and its anticoagulant property can meet clinical requirement [Zhang Minghua, Zheng Haiyan, the blood of anticoagulant biomaterial Liquid phase capacitive, Chinese Tissue Engineering Study, 2013,17 (8), 1505]；In addition, the materials system such as 316L stainless steel, medical cobalt alloy Be easy to produce proliferation of smooth muscle after standby intravascular stent implantation, be easy to cause as after intravascular stent implantation restenosis [Liu Zhangqi, Li Chunliang, the modified hyperplasia with endangium in vascular stent material surface, Chinese Tissue Engineering Study and clinical rehabilitation, 2010, 14 (25), 4721]；Bacterium infection, advanced thrombus and proliferation of smooth muscle are easy to cause graft failure, increase medical instrument and people The risk of work organ implantation.
Copper (Cu) is one of minor metallic element needed by human, and material containing Cu has a good biocompatibility, Cu and The intrauterine device of its alloy preparation, which clinically has, widely to be applied；Numerous studies prove that Cu not only has certain resist Bacterium performance, and certain density Cu ion also has the ability for promoting endothelial cell proliferation and improving body angiogenesis, from And enhance impaired body tissue self-regeneration function [C.G é rard, L.J.Bordeleau, J.Barralet, C.J.Doillona,Biomaterials.2010,31,824；Hu,G.F.Cell.Biochem.1998,69,326]；In addition, Cu ion can be catalyzed the release such as nitric oxide (NO) donor such as RSNO in blood nitric oxide [H Ren, J.F.Wu, C W.Xi,N.Lehnert,T Major,R.H.Bartlett,M.E.Meyerhoff,ACS Appl.Mater.Interfaces.2014,6:3779]；Nitric oxide, which has, to be inhibited platelet activation and aggregation, inhibits smooth The effects of muscle cell multiplication, inhibition leukocyte adhesion [A.de Mel, F.Murad, A.M.Seinfeldian, Chem.Rev.2011,111,5742]。
Have not been reported the Ti-Cu-N for being catalyzed release NO of the method preparation using physical vapour deposition (PVD) both at home and abroad at present Coating also has no the Ti-Cu-N coating of the multifunctional performance with antibacterial, anticoagulation and anti-proliferation of smooth muscle.Although both at home and abroad Have by Ti-Cu type coating be applied to antibacterial or anticoagulation etc. research document, such as document [H.Wu, X.Zhang, X.He,M.Li,X.Huang,R.Hang,B.Tang,Appl.Surf.Sci.2014,317,614；C.Bergemann, S.Zaatreh,K.Wegner,K.Arndt,A.Podbielski,R.Bader,C.Prinz,U.Lembke,J.B.Nebe, World J Transplant 2017 June 24；7 (3): 193-202] in, researcher is heavy using physical gas-phase deposite method Ti-Cu-N coating is accumulated, but they only have studied anti-microbial property, osteoblast compatibility, has been not directed to anticoagulation function, resists The research such as proliferation of smooth muscle, endothelial cell behavior；Document [H.Q.Liu, C.J.Pan, S.J.Zhou, J.F.Li, N.Huang, L.H.Dong, Mater.Sci.Eng., C.2016,69,1175. cathode arc source deposition method preparation Ti-Cu is used in] to apply Layer finds behavior of this coating with anticoagulation and promotion endothelial cell, but is not directed to NO catalysis release, antibacterial and resists flat The performances such as sliding flesh hyperplasia；Patent [title: in-situ plasma coating Ti/Cu composite coating technique, application publication number CN 102094173 A] it is related to a kind of coating containing Cu, Ti, but they use magnetron sputtering technique, first prepare Ti coating and make again Standby Cu coating, forms Ti/Cu metal composite coating, and the method is applied to fusion reactor in face of the compound of plasma facing materials The preparation of coating is not directed to the application in terms of medical instrument；A kind of another patent [title: medical device coatings and its system Preparation Method and the medical instrument containing the coating, 103007361 A of application publication number CN] also it is related to a kind of painting containing Cu, Ti Layer, but it belongs to copper titanium composite coating, does not adulterate N and forms Inorganic and Nonmetallic Coating, and this patent does not show Cu Doping, coating does not have antibacterial action, without nitric oxide (NO) catalysis release, and this coating inhibits endothelialization mistake Journey is only applicable to the medical instrument with very thin nickel-titanium alloy parts being temporarily implanted.
Summary of the invention
In view of the above deficiency of the prior art, the purpose of the present invention is introduce Cu to have good biocompatibility and mechanics In the Ti-N coating system of performance, by changing the ingredient and structure of these coatings, controlled release Cu ion and catalysis release NO, Achieve the purpose that antibacterial, anticoagulation and anti-proliferation of smooth muscle, with solve medical instrument and artificial organs implantation after bacterium infection, The problems such as thrombosis, restenosis hyperplasia.
The technical solution adopted by the present invention is that: a kind of cardiac vascular medical instrument with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood The preparation method of surface Ti-Cu-N coating forms the method for Cu, Ti, N ion and atom in cardiac vascular medical instrument in a vacuum Surface prepares Ti-Cu-N coating, and the doping of Cu is 4-50at% in coating；It is described in a vacuum formed Cu, Ti, N ion and The method of atom includes magnetron sputtering method and metallic cathode arc source sedimentation；Target selection Ti-Cu mosaic target, Ti and the bis- targets of Cu, One of Ti-Cu alloys target.
Further, using magnetron sputtering, comprising the following steps:
A, cardiovascular implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 0.5 × 10- 3Pa–2.0×10-3Pa；Be passed through into vacuum chamber argon gas until pressure be 0.5Pa-2.0Pa, plasma is formed by glow discharge Body carries out workpiece and sputtering target respectively sputter clean 5-100 minutes, is then shut off argon gas and power supply；
B, it is 2/60-16/60, air pressure 0.05- that the application -50V bias on workpiece, nitrogen and argon gas, which are passed through ratio, 2.0Pa；DC power supply is connect on target and is opened, and the power density adjusted on target is about 0.5-10w/cm2, in cardiovascular implanting device Target product Ti-Cu-N coating is made in tool surface.
When the target is Ti-Cu mosaic target, the area ratio of Cu/ (Cu+Ti) is 0.5-30% in target, and power is close on target Degree is 0.5-4.5w/cm2；
When the target is Ti-Cu alloys target, the content of Cu is that 0.5-30at% cathode target power output is close in Ti-Cu alloys target Degree is 1.2-10w/cm2；
When the sputtering target material is Ti and Cu bis- targets, high power and DC sputtering power on Ti target and Cu target respectively； The power density of Ti target is 4.0-10w/cm2；The average power density of Cu target is 0.5-6w/cm2。
When further, using cathode arc source, preparation process is divided into two steps and carries out to obtain the doping of Cu as 15at% Ti-Cu-N coating:
A, vacuum chamber is to 2 × 10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, application -1000V's DC voltage, glow discharge form plasma, carry out sputter clean 10-100 minutes, are then shut off to cardiovascular implantation instrument DC power supply；Adjusting argon pressure is 0.5Pa, adds DC sputtering power, sputtering current respectively on sputtering target Cu target and Ti target 3A generates plasma after forming glow discharge, cleans target 5-30 minutes, be then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；It adopts Ti-Cu-N coating is prepared with cathode arc source deposition method, cathode target uses Ti-Cu mosaic target, the area of Cu/ (Cu+Ti) in target Ratio is 10%；Ti-Cu mosaic target connects DC power supply, and power density is about 4w/cm2。
Using the solution of the present invention, beneficial effect is apparent that
Ti-Cu-N coating release Cu ion prepared by the present invention and catalysis release NO, have antibacterial, anticoagulation and resist smooth The effect of flesh hyperplasia；Bacterium infection, thrombus after can solving medical instrument and artificial organs implantation for cardiac vascular medical instrument The problem of formation, restenosis hyperplasia, improves the using effect of implantation instrument and artificial organs, improves the quality of life of patient；It removes Except this, preparation method is easy to operate, preparation cost is low, and film-forming process is simple, cheap, and preparation process environmental protection is not easy to make Matrix deformation.
Detailed description of the invention
Fig. 1 is in the surface topography behind Ti-Cu-N coating surface Cultured endothelial cell 1 day for mixing that Cu amount is 4at%.
Specific embodiment
The present invention is further described combined with specific embodiments below.
A kind of preparation method of the Ti-Cu-N coating for cardiac vascular medical equipment surfaces, comprising the following steps:
A, cardiovascular implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 0.5 × 10- 3Pa–2.0×10-3Pa；Be passed through into vacuum chamber argon gas until pressure be 0.5Pa-2.0Pa, plasma is formed by glow discharge Body carries out workpiece and sputtering target respectively sputter clean 5-100 minutes, is then shut off argon gas and power supply；
B, it is 2/60-16/60, air pressure 0.05- that the application -50V bias on workpiece, nitrogen and argon gas, which are passed through ratio, 2.0Pa；DC power supply is connect on target and is opened, and the power density adjusted on target is about 0.5-10w/cm2, in cardiovascular implanting device Target product Ti-Cu-N coating is made in tool surface；Wherein Cu doping is 5-50at%.
Wherein preparation method can use magnetically controlled DC sputtering, and high-power impulse magnetron sputtering can also be used, can also adopt With metallic cathode arc source deposition method.
Embodiment 1
A kind of preparation method of the Ti-Cu-N coating for cardiac vascular medical equipment surfaces, comprising the following steps:
A, vitallium angiocarpy implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber is extremely 2.0×10-3Pa；Argon gas is passed through into vacuum chamber until pressure is 2.0Pa；The DC voltage of application -1000V on workpiece leads to It crosses glow discharge and forms plasma, workpiece and sputtering target are carried out sputter clean 10-100 minutes respectively, are then shut off electricity Source；Adjusting argon pressure is 0.5Pa, and on Ti-Cu mosaic target plus DC sputtering power, sputtering current 3A form glow discharge After generate plasma, clean target 5-30 minutes, be then shut off argon gas and power supply；
B, it is 6/40 that the application -50V bias on workpiece, nitrogen and argon gas, which are passed through ratio, air pressure 0.5Pa；Adjust Ti-Cu Mosaic target, the area ratio that Cu/ (Cu+Ti) in target is arranged is about 2.3%；DC power supply is connected on target and is opened, and target is adjusted On power density be about 4.5w/cm2, target product Ti-Cu-N is made on vitallium angiocarpy implantation instrument surface and applies Layer；Wherein the doping of Cu is about 4at%.
Fig. 1 is in the surface topography behind Ti-Cu-N coating surface Cultured endothelial cell 1 day for mixing that Cu amount is 4at%.? Mix the cell-surface engineering after Cu amount is about surface Cultured endothelial cell 1 day of Ti-Cu-N coating of 4at% (Rhodamine 123 and After DAPI dyeing, 200 ×).Its surface has good endothelial cell compatibility as the result is shown.In addition, when additional NO donor is trained When supporting, coating can obviously inhibit the activity of smooth muscle, and inhibit the adherency and activation of blood platelet.
Embodiment 2
A kind of preparation method of the Ti-Cu-N coating for cardiac vascular medical equipment surfaces, comprising the following steps:
A, stainless steel angiocarpy implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 2 × 10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, the DC voltage of application -1000V, glow discharge form plasma Body carries out cardiovascular implantation instrument sputter clean 10-100 minutes, is then shut off DC power supply；Adjusting argon pressure is 0.5Pa adds DC sputtering power, sputtering current 3A, generation etc. after formation glow discharge respectively on sputtering target Cu target and Ti target Gas ions clean target 5-30 minutes, are then shut off argon gas and power supply；
B, argon gas and nitrogen are each led into vacuum chamber, nitrogen and argon gas ratio are 10/60, until pressure 0.5Pa；? The substrate bias of application -50V on cardiovascular implantation instrument；It is positioned to Cu target, Ti target to be mutually 90 degree, respectively in Cu target and Ti target It is upper to add high power and DC sputtering power；Ti target sputtering current is 2A, and the power density of Ti target is 5.0w/cm2；Adjust Cu target Average power density be about 1w/cm2, Cu target voltage is 600V, and frequency 100Hz, pulsewidth is 50 μ s；It is planted in stainless steel blood vessel Enter equipment surfaces and target product Ti-Cu-N coating is made, wherein the doping of Cu is about 16at%.
Embodiment 3
A kind of preparation method of the Ti-Cu-N coating for cardiac vascular medical equipment surfaces, comprising the following steps:
A, stainless steel angiocarpy implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 2 × 10-3Pa is passed through argon gas into vacuum chamber until pressure is 2.0Pa；Add DC power supply on workpiece, forms glow discharge generation etc. Gas ions carry out cardiovascular implantation instrument sputter clean 10-100 minutes, close DC power supply；Adjusting argon pressure is 0.5Pa adds DC sputtering power on Ti-Cu mosaic target；Sputtering current 3A generates plasma after forming glow discharge, clearly It washes target 5-30 minutes, is then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；It adjusts The content for saving Cu in Ti-Cu alloys target is 10at%；In alloys target plus DC power supply, the power density for adjusting cathode target are 6.0w/cm2, sputtering current 3A；Target product Ti-Cu-N coating is made on stainless steel implantation instrument surface；In gained coating The doping of Cu is about 30at%.
Embodiment 4
A kind of preparation method of the Ti-Cu-N coating for cardiac vascular medical equipment surfaces, comprising the following steps:
A, stainless steel angiocarpy implantation instrument workpiece is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber is extremely 2×10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, the DC voltage of application -1000V, glow discharge are formed Gas ions carry out workpiece sputter clean 10-100 minutes, are then shut off DC power supply；Adjusting argon pressure is 0.5Pa, On Ti-Cu mosaic target plus DC sputtering power, sputtering current 3A generate plasma after formation glow discharge, clean target 5- 30 minutes, it is then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；It adjusts The area ratio for saving Cu/ (Cu+Ti) in Ti-Cu mosaic target is 10at%；Ti-Cu mosaic target connects DC power supply, power density For 0.5w/cm2；The doping of gained coating Cu is about 40at%.
Embodiment 5
A, polyformaldehyde angiocarpy implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 2 × 10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, the DC voltage of application -1000V, glow discharge form plasma Body carries out cardiovascular implantation instrument sputter clean 10-100 minutes, is then shut off DC power supply；Adjusting argon pressure is 0.5Pa adds DC sputtering power, sputtering current 3A, generation etc. after formation glow discharge respectively on sputtering target Cu target and Ti target Gas ions clean target 5-30 minutes, are then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；It adjusts The area ratio for saving Cu/ (Cu+Ti) in Ti-Cu mosaic target is 10at%；Ti-Cu mosaic target connects DC power supply, power density For 0.5w/cm2；Workpiece uses high polymer angiocarpy implantation instrument, and the doping of gained coating Cu is 20at%.
Embodiment 6
A, stainless steel angiocarpy implantation instrument is put into the vacuum chamber of cathode arc source equipment, vacuum chamber to 2 × 10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, the DC voltage of application -1000V, glow discharge form plasma Body carries out cardiovascular implantation instrument sputter clean 10-100 minutes, is then shut off DC power supply；Adjusting argon pressure is 0.5Pa adds DC sputtering power, sputtering current 3A, generation etc. after formation glow discharge respectively on sputtering target Cu target and Ti target Gas ions clean target 5-30 minutes, are then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；It adopts Ti-Cu-N coating is prepared with cathode arc source deposition method, cathode target uses Ti-Cu mosaic target, the area of Cu/ (Cu+Ti) in target Ratio is 10%；Ti-Cu mosaic target connects DC power supply, and power density is about 4w/cm2；Workpiece uses metal and alloy painstaking effort Pipe implantation instrument, the doping of Cu is about 15at% in gained coating.
Because of the performance that Cu has antibacterial, promotes endothelial cell growth, promotes tissue repair, Cu also has catalysis NO release To inhibit the special physiological function of platelet activation and aggregation, inhibition smooth muscle cell proliferation, inhibition leukocyte adhesion etc., this hair Bright preparation Ti-Cu-N coating is modified applied to cardiovascular devices surface, by changing the ingredient and structure of these coatings, realizing controlled-release Cu ion and catalysis release NO are put, achievees the purpose that antibacterial, anticoagulation and anti-proliferation of smooth muscle, to solve medical instrument and artificial Organ implantation after bacterium infection, thrombosis, restenosis hyperplasia the problems such as.
The Ti-Cu-N that we prepare is Inorganic and Nonmetallic Coating, by way of transformation preparation method, transformation target, sputtering, Depositional model, gas mode etc. carry out process control and optimize, to obtain Cu doping ratio in 5-50at%, structure as nanometer Brilliant coating, the coating can controlled release Cu ion NO, promote endothelial cell growth, reach antibacterial, anticoagulation and anti-smooth The purpose of flesh hyperplasia；For example, by using different preparation methods such as magnetically controlled DC sputtering, high-power impulse magnetron sputtering, metallic cathode Arc source deposition；Target can choose Ti-Cu combination target or the bis- targets of Ti, Cu, Ti-Cu alloys target；Method prepared by the present invention belongs to Low Temperature Plasma Treating, film-forming process is simple, and Costco Wholesale is cheap, preparation process environmental protection, is not easy to can solve matrix deformation These medical instruments be chronically implanted after generation bacterium infection, thrombosis, restenosis hyperplasia the problems such as, involved side Method is suitable for metal, alloy, high polymer medical instrument, to prepare the coating of similar function.

Claims (4)

1. a kind of preparation side of the cardiac vascular medical equipment surfaces Ti-Cu-N coating with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood Method, which is characterized in that the method for forming Cu, Ti, N ion and atom in a vacuum prepares Ti- in cardiac vascular medical equipment surfaces Cu-N coating, the doping of Cu is 4-50at% in coating；The method packet for forming Cu, Ti, N ion and atom in a vacuum Include magnetron sputtering method and metallic cathode arc source sedimentation；In target selection Ti-Cu mosaic target, Ti and the bis- targets of Cu, Ti-Cu alloys target One kind.
2. the cardiac vascular medical equipment surfaces Ti-Cu- according to claim 1 with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood The preparation method of N coating, which is characterized in that use magnetron sputtering；The following steps are included:
A, cardiovascular implantation instrument is put into the vacuum chamber of magnetron sputtering apparatus, vacuum chamber to 0.5 × 10-3Pa–2.0 ×10-3Pa；Argon gas is passed through into vacuum chamber until pressure is 0.5Pa-2.0Pa, by glow discharge formation plasma, to work Part and sputtering target carry out sputter clean 5-100 minutes respectively, are then shut off argon gas and power supply；
B, it is 2/60-16/60, air pressure 0.05-2.0Pa that the application -50V bias on workpiece, nitrogen and argon gas, which are passed through ratio,；? DC power supply is connect on target and is opened, and the power density adjusted on target is about 0.5-10w/cm2, in cardiovascular implantation instrument surface system Obtain the target product Ti-Cu-N coating that Cu doping is 5-50at%.
3. the cardiac vascular medical equipment surfaces Ti-Cu- according to claim 2 with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood The preparation method of N coating, which is characterized in that when the target is Ti-Cu mosaic target, the area ratio of Cu/ (Cu+Ti) is in target 0.5-30%, power density is 0.5-4.5w/cm on target2；
When the target is Ti-Cu alloys target, the content of Cu is that 0.5-30at% cathode target power density is in Ti-Cu alloys target 1.2-10w/cm2；
When the sputtering target material is Ti and Cu bis- targets, high power and DC sputtering power on Ti target and Cu target respectively；Ti target Power density be 4.0-10w/cm2；The average power density of Cu target is 0.5-6w/cm2。
4. the cardiac vascular medical equipment surfaces Ti-Cu- according to claim 1 with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood The preparation method of N coating, which is characterized in that when using cathode arc source, preparation process is divided into two steps and carries out to obtain the doping of Cu Amount is the Ti-Cu-N coating of 15at%:
A, vacuum chamber is to 2 × 10-3Pa；Argon gas is passed through into vacuum chamber until pressure 2.0Pa, the direct current of application -1000V Voltage, glow discharge form plasma, carry out sputter clean 10-100 minutes to cardiovascular implantation instrument, are then shut off direct current Power supply；Adjusting argon pressure is 0.5Pa, adds DC sputtering power, sputtering current 3A, shape respectively on sputtering target Cu target and Ti target At plasma is generated after glow discharge, cleans target 5-30 minutes, be then shut off argon gas and power supply；
B, on workpiece application -50V bias, be passed through argon gas and nitrogen, adjust nitrogen and argon gas ratio is 10/60；Using yin Polar arc source deposition method prepares Ti-Cu-N coating, and cathode target uses Ti-Cu mosaic target, the area ratio of Cu/ (Cu+Ti) in target It is 10%；Ti-Cu mosaic target connects DC power supply, and power density is about 4w/cm2。
CN201910393873.6A 2019-05-10 2019-05-10 The preparation method of cardiac vascular medical equipment surfaces Ti-Cu-N coating with the anti-proliferation of smooth muscle of antibiosis anticoagulative blood Pending CN110129748A (en)

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