CN107587102A - A kind of doping metals ceramic membrane biomaterial, preparation method and applications - Google Patents

A kind of doping metals ceramic membrane biomaterial, preparation method and applications Download PDF

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Publication number
CN107587102A
CN107587102A CN201710710281.3A CN201710710281A CN107587102A CN 107587102 A CN107587102 A CN 107587102A CN 201710710281 A CN201710710281 A CN 201710710281A CN 107587102 A CN107587102 A CN 107587102A
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ceramic membrane
vacuum
doping metals
workpiece
biomaterial
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冷永祥
邓乔元
谢东
黄楠
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Southwest Jiaotong University
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Southwest Jiaotong University
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Abstract

The invention discloses a kind of doping metals ceramic membrane biomaterial, preparation method and applications, the atomic percent of doped metallic elements is 1% ~ 10% in the ceramic membrane biomaterial of doping metals;The ceramic membrane biomaterial of doping metals is prepared using damascene target by a kind of method in reaction magnetocontrol sputtering, metal arc source deposition and ion-plating deposition;For the abrasion self-lubricating in artificial organs friction pair in vivo environment, the wear resistance of material can be increased, improve the service life of artificial organs in environment in vivo;The present invention is not easy to deform upon medicine equipment, and preparation process is easy, environmentally friendly, cost is low.

Description

A kind of doping metals ceramic membrane biomaterial, preparation method and applications
Technical field
The present invention relates to technical field of biological material, and in particular to a kind of doping metals ceramic membrane biomaterial, preparation method And its application.
Background technology
The medicine equipments such as the artificial intervertebral disk of implantation within a patient, joint prosthesis need to be on active service 10 years in patient with On, the head of implantation instrument-mortar structure Relative friction motion is up to tens million of times during military service;Abrasion can produce caused by friction Various abrasive dusts and metal ion;And then inflammatory reaction and medicine equipment is caused to fail;Such as:Matevz Topolovec, Andrej C,Ingrid Milos.Metal-on-metal vs.metal-on-polyethylene total hip arthroplasty tribological evaluation of retrieved components and periprosthetic tissue.journal of the mechanical behavior of biomedical materials 34(2014)243–252;The method being modified by surface improves implanted medical device in vivo wear-resistant, Corrosion resistant performance, existing correlative study, such as rubbed in joint prosthesis and prepare nitride film (CrN, TiN with secondary surface Deng);Ortega-Saenz,M.A.L.Hernandez-Rodrigueza,V.Ventura-Sobrevilla, R.Michalczewski,J.Smolik,M.Szczerek.Wear 271(2011)2125–2131;F.Yildiz, A.F.Yetim,A.Alsaran,I.Efeoglu.Wear 267(2009)695–701;But the nitride layer friction system formed Number is larger, limited to joint wear resistance increase rate.
The content of the invention
The present invention discloses the doping metals ceramic membrane biology material in a kind of environment in vivo with abrasion self-lubricating function Material, preparation method and applications.
The technical solution adopted by the present invention is:A kind of doping metals ceramic membrane biomaterial, the ceramic thin of doping metals The atomic percent of doped metallic elements is 1%~10% in film biomaterial.
Further, the ceramic membrane of the doping metals is the TiN ceramic membrane biomaterials Cu- of doping metals copper TiN, doping metals copper TiO2Ceramic membrane biomaterial Cu-TiO2, doping metals copper CrN ceramic membrane biomaterials Cu- CrN, the TiN ceramic membrane biomaterials Ag-TiN of doping metals silver, the CrN ceramic membrane biomaterials Ag- of doping metals silver CrN, doping metals nickel TiN ceramic membrane biomaterial Ni-TiN, the TiN ceramic membrane biomaterials Cr- of doping metals chromium One kind in TiN.
Further, the ceramic membrane biomaterial of the doping metals is splashed using damascene target by reacting magnetic control Penetrate, prepared by a kind of method in metal arc source deposition and ion-plating deposition.
Further, the matrix of the ceramic membrane biomaterial of the doping metals is vitallium, stainless steel, titanium conjunction One kind in gold.
Further, a kind of preparation method of doping metals ceramic membrane biomaterial, comprises the following steps:
A, it is placed in vacuum after the cleaning of artificial organs friction of workpiece secondary surface and is at least 3 × 10-3In Pa vacuum chamber;Xiang Zhen Argon gas is passed through in empty room, gas pressure in vacuum is reached 0.5~2.0Pa;Apply 800~1000V DC negative bias voltages in workpiece surface, Glow discharge forms plasma;Then 30 minutes sputter cleans are carried out to workpiece surface, closes argon gas;Argon is passed through to vacuum chamber Gas, it is 0.5~2.0Pa to make gas pressure in vacuum, applies 3A electric currents, -200V~-500V voltages, to damascene target on target Material carries out 20 minutes sputter cleans, closes bias generator afterwards, closes argon gas;
B, continue to be passed through into vacuum chamber containing argon gas, gas pressure in vacuum is reached 0.5~2.0Pa;Apply -10 on workpiece ~-100V bias, shielding power supply is opened, damascene target sputtering mean power is 1W/cm2~3W/cm2, in substrate work-piece table Face had both obtained the ceramic membrane biomaterial of gold doping category.
Further, the doping metals ceramic membrane biomaterial is in artificial organs friction pair in vivo environment Wear self-lubricating.
Further, the doping metals ceramic membrane biomaterial promotes in artificial organs friction pair in vivo environment Frictional interface forms protein biology film, is further converted to graphite lubrication layer.
Further, the doping metals ceramic membrane biomaterial can increase in artificial organs friction pair in vivo environment Add the wear resistance of material.
Further, the doping metals ceramic membrane biomaterial improves in artificial organs friction pair in vivo environment The service life of artificial organs.
The beneficial effects of the invention are as follows:
(1) the ceramic membrane biomaterial of doping metals prepared by the present invention reduces ceramic membrane biomaterial friction and matched somebody with somebody Coefficient of friction between pair, the modifying artificial organ friction of ceramic membrane biomaterial is added with secondary wear resistance;
(2) doping metals ceramic membrane biomaterial prepared by the present invention can be used for the surface of different materials to be modified;
(3) preparation method of the present invention is applied to various medicine equipments, medicine equipment will not be caused to deform upon, and prepared Journey is simple and environmentally-friendly, cost is low.
Brief description of the drawings
Fig. 1 is reaction magnetocontrol sputtering equipment schematic in the present invention.
Fig. 2 is the polishing scratch profile diagram of Cu-TiN and TiAlN thin film in protein solution.
Fig. 3 is Cu-TiN and TiAlN thin film the Raman testing result after fretting wear in protein solution.
Fig. 4 is cathode arc source film deposition equipment schematic diagram.
Fig. 5 is that Cu-TiN films grind ToF-SIMS testing results inside and outside spot in protein solution after fretting wear.
Embodiment
The present invention will be further described with specific embodiment below in conjunction with the accompanying drawings.
A kind of doping metals ceramic membrane biomaterial, doped metallic elements in the ceramic membrane biomaterial of doping metals Atomic percent be 1%~10%;The ceramic membrane of the doping metals is the TiN ceramic membrane biology materials of doping metals copper Expect Cu-TiN, the TiO of doping metals copper2Ceramic membrane biomaterial Cu-TiO2, doping metals copper CrN ceramic membrane biology materials Expect Cu-CrN, the TiN ceramic membrane biomaterials Ag-TiN of doping metals silver, the CrN ceramic membrane biology materials of doping metals silver Expect Ag-CrN, the TiN ceramic membrane biomaterial Ni-TiN of doping metals nickel, the TiN ceramic membrane biology materials of doping metals chromium Expect one kind in Cr-TiN
Further, the ceramic membrane biomaterial of the doping metals is splashed using damascene target by reacting magnetic control Penetrate, prepared by a kind of method in metal arc source deposition and ion-plating deposition;Existed using damascene target by reaction magnetocontrol sputtering Artificial organs friction of workpiece secondary surface prepares the ceramic membrane biomaterial of doped metallic elements;The ceramic thin of doped metallic elements The atomic percent of doped metallic elements is 1%~10% in film biomaterial;Preparation method can also be sunk using metal arc source Product method, the content of doped metallic elements can be regulated and controled by the embedded with metal bar quantity changed in mosaic target;Metal Mosaic target is following one kind or at least two:Copper titanium target, silver-colored titanium target, copper chromium target, silver-colored chromium target, nickel chromium triangle target;Artificial organs workpiece Friction is with secondary one kind in vitallium, stainless steel, titanium alloy.
A kind of preparation method of doping metals ceramic membrane biomaterial, comprises the following steps:
A, it is placed in vacuum after the cleaning of artificial organs friction of workpiece secondary surface and is at least 3 × 10-3In Pa vacuum chamber;Xiang Zhen Argon gas is passed through in empty room, gas pressure in vacuum is reached 0.5~2.0Pa;Apply 800~1000V DC negative bias voltages in workpiece surface, Glow discharge forms plasma;Then 30 minutes sputter cleans are carried out to workpiece surface, closes argon gas;Argon is passed through to vacuum chamber Gas, it is 0.5~2.0Pa to make gas pressure in vacuum, applies 3A electric currents, -200V~-500V voltages, to damascene target on target Material carries out 20 minutes sputter cleans, closes bias generator afterwards, closes argon gas;
B, continue to be passed through into vacuum chamber containing argon gas, gas pressure in vacuum is reached 0.5~2.0Pa;Apply -10 on workpiece ~-100V bias, shielding power supply is opened, metallic target sputtering mean power is 1W/cm2~3W/cm2, on substrate work-piece surface both Obtain the ceramic membrane biomaterial of gold doping category.
The gas being passed through in step B into vacuum chamber, can be Ar/N2、Ar/O2、Ar/CO2Etc. mixed gas.
Further, the doping metals ceramic membrane biomaterial is in artificial organs friction pair in vivo environment Wear self-lubricating.
Further, the doping metals ceramic membrane biomaterial promotes in artificial organs friction pair in vivo environment Frictional interface forms protein biology film, is further converted to graphite lubrication layer.
Further, the doping metals ceramic membrane biomaterial can increase in artificial organs friction pair in vivo environment Add the wear resistance of material.
Further, the doping metals ceramic membrane biomaterial improves in artificial organs friction pair in vivo environment The service life of artificial organs.
The method of the present invention also can more meticulously be expressed as following scheme:
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and Vacuum is evacuated to 3 × 10 by molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 0.5~2.0Pa to make gas pressure in vacuum, in workpiece table Face applies 800~1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Be passed through argon gas to vacuum chamber, make gas pressure in vacuum for 0.5~ 2.0Pa, apply 3A electric currents on target, -200V~-500V voltages, 20 minutes sputter cleans are carried out to damascene target, it After close bias generator, close argon gas.
B, argon gas is passed through to vacuum chamber, it is 0.5~2.0Pa to make gas pressure in vacuum, applies -10~-100V's on substrate Dc bias, is then turned on shielding power supply, and the sputtering mean power on damascene target is 1W/cm2~3W/cm2;Prepare doping The ceramic membrane biomaterial of metal, the atomic percent of metallic element is 1%~10%.
The ceramic membrane biomaterial prepared using the present invention, by the metal member that certain content is adulterated in ceramic membrane Element so that during ceramic membrane biomaterial is on active service in human body, discharge metal ion, metal ion catalysis vivo environment Middle biomolecule denaturation, it is adsorbed onto frictional interface;The biomolecule of denaturation is degraded into stone under frictional interface shearing force Layer of ink, the ceramic membrane biomaterial surface worn is covered in, reduces friction with the coefficient of friction between pair, reach friction The purpose of self-lubricating;With the progress of abrasion, biomolecule degrade to be formed graphite linings abrasion complete, expose fresh ceramics Thin film bio material;Reuse the abrasion of ceramic membrane biomaterial and discharge metal ion promotion ceramic membrane biomaterial table Face protein adsorption, denaturation, decomposition, formation graphite linings;It is covered in the ceramic membrane biomaterial surface worn;Continuous By the degraded of Metal ion release, catalysis biological molecule in friction process, graphite linings are constantly formed to ceramic membrane biology material Material plays lubrication;So that ceramic membrane biomaterial has self-lubricating function in vivo, artificial organs friction pair is improved The life-span of surface ceramic thin film bio material and long-time stability.
Embodiment 1
The preparation method of doping metals ceramic membrane biomaterial is as follows:
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 800V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -200V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Cu-Ti mosaic targets (20 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -90V Dc bias, is then turned on shielding power supply on substrate, the application -600V voltages on Cu-Ti mosaic targets, regulation Mosaic target sputtering mean power is 1W/cm2, prepare the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper, the original of Cu elements Sub- percentage is 1%.
Fig. 1 is the equipment schematic diagram of the example method, and increase and decrease can be passed through by mixing the copper content of copper titanium nitride (Cu-TiN) film Copper rod quantity in mosaic target regulates and controls;Fig. 2 is the polishing scratch profile diagram of Cu-TiN and TiAlN thin film in protein solution, Ke Yifa The wearability of the Cu-TiN films of existing reactive magnetron sputtering is better than the wearability of general T iN films;Illustrate in Cu-TiN Cu elements in film promote the protein denaturation in solution and are adsorbed onto friction circle by wearing release into protein solution Face, the wear extent of frictional interface is reduced, so as to be effectively increased its anti-wear performance in Physiological Medium.
Embodiment 2
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 800V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -400V voltages, 30 minutes sputter cleans are carried out to Cu-Ti mosaic targets (150 copper rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -50V Dc bias, is then turned on shielding power supply on substrate, the application -800V voltages on Cu-Ti mosaic targets, regulation Mosaic target sputtering mean power is 3W/cm2, prepare the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper, the original of Cu elements Sub- percentage is 10%.
Fig. 3 simulates fretting wear in physiological environment in vitro respectively for the Cu-TiN and TiAlN thin film prepared in the present embodiment After experiment, the result of Raman detection is carried out respectively to polishing scratch inside;Raman results show that Cu-TiN polishing scratch has very strong drawing Graceful activity, particularly at 1360cm-1 and 1560cm-1 wave numbers, produce obvious Raman scattering signal, and TiN polishing scratch Do not have Raman active in the wave number;Show that degraded occurs at Cu-TiN film polishing scratch and generates unformed rich carbon for protein Lubricating layer, wear surface can be played a part of to lubricate anti-attrition.
Embodiment 3
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -200V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Cu-Ti mosaic targets (70 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -50V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Cu-Ti mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper, the original of Cu elements Sub- percentage is 8%.
Embodiment 4
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -200V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ti-Cu mosaic targets (40 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -80V Dc bias, is then turned on shielding power supply on substrate, the application -600V voltages on Ti-Cu mosaic targets, regulation Mosaic target sputtering mean power is 1W/cm2, prepare the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper, the original of Cu elements Sub- percentage is 2%.
Embodiment 5
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -200V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ti-Cu mosaic targets (90 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -100V Dc bias, is then turned on shielding power supply on substrate, the application -600V voltages on Ti-Cu mosaic targets, adjusts It is 2W/cm to save mosaic target sputtering mean power2, the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper is prepared, Cu elements Atomic percent is 8%.
Embodiment 6
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -80V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ti-Cu mosaic targets (80 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -80V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ti-Cu mosaic targets, regulation Mosaic target sputtering mean power is 1.5W/cm2, the TiAlN thin film biomaterial (Cu-TiN) of doping metals copper is prepared, Cu elements Atomic percent is 6%.
Embodiment 7
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 900V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ti-Cu mosaic targets (50 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/O to vacuum chamber2Mixed gas (SCCMAr:SCCMO2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -100V Dc bias, is then turned on shielding power supply on substrate, the application -600V voltages on Ti-Cu mosaic targets, adjusts It is 1W/cm to save mosaic target sputtering mean power2, prepare the TiO of doping metals copper2Thin film bio material C u-TiO2, Cu elements Atomic percent is 3%.
Embodiment 8
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans are carried out to Ti-Cu mosaic targets (120 copper rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/O to vacuum chamber2Mixed gas (SCCMAr:SCCMO2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -50V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ti-Cu mosaic targets, regulation Mosaic target sputtering mean power is 3W/cm2, prepare the TiO of doping metals copper2Thin film bio material C u-TiO2, the original of Cu elements Sub- percentage is 10%.
Embodiment 9
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1100V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans are carried out to Ti-Cu mosaic targets (100 copper rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/O to vacuum chamber2Mixed gas (SCCMAr:SCCMO2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -90V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ti-Cu mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare the TiO of doping metals copper2Thin film bio material C u-TiO2, the original of Cu elements Sub- percentage is 9%.
Embodiment 10
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ti-Cu mosaic targets (20 copper rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/O to vacuum chamber2Mixed gas (SCCMAr:SCCMO2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -70V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ti-Cu mosaic targets, regulation Mosaic target sputtering mean power is 1.5W/cm2, prepare the TiO of doping metals copper2Thin film bio material C u-TiO2, Cu elements Atomic percent is 1%.
Embodiment 11
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 800V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ag-Ti mosaic targets (40 silver-colored rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -70V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ag-Ti mosaic targets, regulation Mosaic target sputtering mean power is 1.5W/cm2, prepare doping metals silver TiAlN thin film biomaterial Ag-TiN, Ag element original Sub- percentage is 6%.
Embodiment 12
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans are carried out to Ag-Ti mosaic targets (120 silver-colored rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:1) it is 1.0Pa, to make gas pressure in vacuum, Application -80V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ag-Ti mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare doping metals silver TiAlN thin film biomaterial Ag-TiN, Ag element atom Percentage is 10%.
Embodiment 13
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ag-Ti mosaic targets (60 silver-colored rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:1) it is 1.0Pa, to make gas pressure in vacuum, Application -70V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ag-Ti mosaic targets, regulation Mosaic target sputtering mean power is 1W/cm2, prepare doping metals silver TiAlN thin film biomaterial Ag-TiN, Ag element atom Percentage is 5%.
Embodiment 14
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 800V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ag-Ti mosaic targets (20 silver-colored rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:1) it is 1.0Pa, to make gas pressure in vacuum, Application -100V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ag-Ti mosaic targets, adjusts It is 1W/cm to save mosaic target sputtering mean power2, prepare doping metals silver TiAlN thin film biomaterial Ag-TiN, Ag element original Sub- percentage is 1%.
Embodiment 15
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ni-Ti mosaic targets (10 nickel rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:2) it is 1.0Pa, to make gas pressure in vacuum, Application -50V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ni-Ti mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare the atom of TiAlN thin film biomaterial Ni-TiN, the Ni element of doping metals nickel Percentage is 1%.
Embodiment 16
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Ni-Ti mosaic targets (60 nickel rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -70V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ni-Ti mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare the atom of TiAlN thin film biomaterial Ni-TiN, the Ni element of doping metals nickel Percentage is 5%.
Embodiment 17
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 800V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans are carried out to Ni-Ti mosaic targets (100 nickel rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -100V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Ni-Ti mosaic targets, adjusts It is 3W/cm to save mosaic target sputtering mean power2, prepare the original of TiAlN thin film biomaterial Ni-TiN, the Ni element of doping metals nickel Sub- percentage is 10%.
Embodiment 18
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans, Zhi Houguan are carried out to Cr-Ti mosaic targets (20 chromium rods) Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -80V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Cr-Ti mosaic targets, regulation Mosaic target sputtering mean power is 2W/cm2, prepare the atom of TiAlN thin film biomaterial Cr-TiN, the Cr element of doping metals chromium Percentage is 1%.
Embodiment 19
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on sample stage, is put into the vacuum chamber of magnetron sputtering apparatus, by fore pump and is divided Vacuum is evacuated to 3 × 10 by sub- pump-3Pa;Argon gas is passed through into vacuum chamber, regulation vacuum pumping speed makes gas pressure in vacuum be 1.0Pa, Workpiece surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 to workpiece surface The sputter clean of minute, bias generator is closed afterwards, close argon gas;Argon gas is passed through to vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, Apply 3A electric currents on target, -100V voltages, 30 minutes sputter cleans are carried out to Cr-Ti mosaic targets (100 chromium rods), afterwards Sputtering source is closed, closes argon gas.
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=2:3) it is 1.0Pa, to make gas pressure in vacuum, Application -70V Dc bias, is then turned on shielding power supply on substrate, the application -700V voltages on Cr-Ti mosaic targets, regulation Mosaic target sputtering mean power is 3W/cm2, prepare the atom of TiAlN thin film biomaterial Cr-TiN, the Cr element of doping metals chromium Percentage is 10%.
Embodiment 20
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 200V back bias voltages on substrate;Vacuum Arc source current is opened, makes Ti metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.5A, cathode voltage 80V to make cathode current;Cu cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.1A, cathode voltage 60V, workpiece is rotated with 60 revs/min of speed, and then realize the uniformly heavy of film Product;Cu-TiN films are deposited on workpiece, its Cu Elements Atoms percentage is 5%.
Fig. 4 is the equipment schematic diagram of Vacuum Arc source depositing device;Fig. 5 simulates physiological environment for Cu-TiN films and rubbed in vitro After scouring damage, the inside and outside ToF-SIMS of mill spot (flight time resolution-SIMS detection) experimental result, as a result Show to grind inside spot than there is the carbon containing low structures such as more C, CH outside mill spot;This explanation is in copper ion and shearing force Under collective effect, the protein in physiological solution is easier that the rich carbon lubricating layer of denaturation degraded generation occurs, and lubrication is played to polishing scratch The effect of anti-attrition.
Embodiment 21
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 200V back bias voltages on substrate;Vacuum Arc source current is opened, makes Ti metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.6A, cathode voltage 80V to make cathode current;Ag cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.1A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Ag-TiN films are deposited on workpiece, its Ag Elements Atoms percentage is 3%.
Embodiment 22
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1100V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 200V back bias voltages on substrate;Vacuum Arc source current is opened, makes Ti metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.5A, cathode voltage 80V to make cathode current;Cu cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.2A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Cu-TiN films are deposited on workpiece, its Cu Elements Atoms percentage is 10%.
Embodiment 23
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1200V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 100V back bias voltages on substrate;Vacuum Arc source current is opened, makes Ti metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.6A, cathode voltage 80V to make cathode current;Ag cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.2A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Ag-TiN films are deposited on workpiece, its Ag Elements Atoms percentage is 6%.
Embodiment 24
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 150V back bias voltages on substrate;Vacuum Arc source current is opened, makes Cr metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.6A, cathode voltage 80V to make cathode current;Cu cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.1A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Cu-CrN films are deposited on workpiece, its Cu Elements Atoms percentage is 4%.
Embodiment 25
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 900V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMN2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 200V back bias voltages on substrate;Vacuum Arc source current is opened, makes Cr metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.6A, cathode voltage 80V to make cathode current;Ag cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.08A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Ag-CrN films are deposited on workpiece, its Ag Elements Atoms percentage is 1%.
Embodiment 26
A, workpiece and target material surface cleaning:Workpiece is being cleaned by ultrasonic 10 minutes respectively in acetone and ethanol, Ran Hou It is dried for standby in air;Workpiece is fixed on metal substrate, is put into the vacuum chamber of cathode vacuum arc source depositing device, passes through Vacuum is evacuated to 3 × 10 by fore pump and molecular pump-3Pa;Argon gas is passed through into vacuum chamber, it is 1.0Pa to make gas pressure in vacuum, in work Part surface applies 1000V DC negative bias voltages, argon gas is produced glow discharge, forms plasma and carries out 30 points to workpiece surface The sputter clean of clock, bias generator is closed afterwards, close argon gas;
B, it is passed through Ar/N to vacuum chamber2Mixed gas (SCCMAr:SCCMO2=1:3) it is 10, to make gas pressure in vacuum-1Pa, Apply 150V back bias voltages on substrate;Vacuum Arc source current is opened, makes Ti metallic cathode ionizations, and produces plasma, is adjusted Power parameter, it is 0.6A, cathode voltage 80V to make cathode current;Ni cathode powers are opened simultaneously, regulation power supply parameter, make the moon Electrode current is 0.1A, cathode voltage 60V, workpiece is rotated with 40 revs/min of speed, and then realize the uniformly heavy of film Product.Ni-TiO is deposited on workpiece2Film, its Ti Elements Atoms percentage are 5%.
Metal in doping metals ceramic membrane biomaterial does not react with ceramic membrane, it is general using Cu be doped to TiN, Effect is best in the films such as CrN;The ceramic membrane biomaterial of doping metals is catalyzed vivo protein by the release of metal ion Being decomposed to form graphite linings reduces the friction of ceramic membrane biomaterial with the coefficient of friction between pair, adds ceramic membrane biology The friction of material modification artificial organs obtains the ceramic membrane biology material with abrasion self-lubricating function with secondary wear-resistant property Material;Ceramic membrane biomaterial can be used for the modification of different materials surface, such as the material such as vitallium, stainless steel, titanium alloy Material;Ceramic membrane biomaterial, can according to different service conditions, by the control of doped metallic elements atomic concentration 1%~ Between 10%;Preparation method belongs to cold-plasma surfaces treated, and suitable material and medicine equipment species are various, are not easy to make doctor Treat apparatus to deform upon, and preparation process is easy, environmentally friendly, cost is low.

Claims (9)

  1. A kind of 1. doping metals ceramic membrane biomaterial, it is characterised in that:Mixed in the ceramic membrane biomaterial of doping metals The atomic percent of miscellaneous metallic element is 1%~10%.
  2. A kind of 2. doping metals ceramic membrane biomaterial according to claim 1, it is characterised in that:The doping metals Ceramic membrane be doping metals copper TiN ceramic membrane biomaterials Cu-TiN, the TiO of doping metals copper2Ceramic membrane is given birth to Thing material C u-TiO2, doping metals copper CrN ceramic membrane biomaterials Cu-CrN, doping metals silver TiN ceramic membranes life Thing materials A g-TiN, the CrN ceramic membrane biomaterials Ag-CrN of doping metals silver, doping metals nickel TiN ceramic membranes life One kind in thing material Ni-TiN, the TiN ceramic membrane biomaterials Cr-TiN of doping metals chromium.
  3. A kind of 3. doping metals ceramic membrane biomaterial according to claim 1, it is characterised in that:The doping metals Ceramic membrane biomaterial using damascene target pass through reaction magnetocontrol sputtering, metal arc source deposition and ion-plating deposition in It is prepared by a kind of method.
  4. A kind of 4. doping metals ceramic membrane biomaterial according to claim 1, it is characterised in that:The doping metals Ceramic membrane biomaterial matrix be vitallium, stainless steel, one kind in titanium alloy.
  5. A kind of 5. preparation method of doping metals ceramic membrane biomaterial as claimed in claim 1, it is characterised in that including Following steps:
    A, it is placed in vacuum after the cleaning of artificial organs friction of workpiece secondary surface and is at least 3 × 10-3In Pa vacuum chamber;To vacuum chamber In be passed through argon gas, gas pressure in vacuum is reached 0.5~2.0Pa;Apply 800~1000V DC negative bias voltages, aura in workpiece surface Electric discharge forms plasma;Then 30 minutes sputter cleans are carried out to workpiece surface, closes argon gas;Argon gas is passed through to vacuum chamber, It is 0.5~2.0Pa to make gas pressure in vacuum, applies 3A electric currents on target, -200V~-500V voltages, damascene target is entered 20 minutes sputter cleans of row, bias generator is closed afterwards, close argon gas;
    B, continue to be passed through into vacuum chamber containing argon gas, gas pressure in vacuum is reached 0.5~2.0Pa;On workpiece apply -10~- 100V bias, shielding power supply is opened, damascene target sputtering mean power is 1W/cm2~3W/cm2, on substrate work-piece surface Both the ceramic membrane biomaterial of gold doping category had been obtained.
  6. A kind of 6. application of doping metals ceramic membrane biomaterial as claimed in claim 1, it is characterised in that:The doping Metallic cermet films biomaterial is for the abrasion self-lubricating in artificial organs friction pair in vivo environment.
  7. A kind of 7. application of doping metals ceramic membrane biomaterial according to claim 6, it is characterised in that:It is described to mix Miscellaneous metallic cermet films biomaterial promotes frictional interface to form protein biology film in artificial organs friction pair in vivo environment, It is further converted to graphite lubrication layer.
  8. A kind of 8. application of doping metals ceramic membrane biomaterial according to claim 6, it is characterised in that:It is described to mix Miscellaneous metallic cermet films biomaterial can increase the wear resistance of material in artificial organs friction pair in vivo environment.
  9. A kind of 9. application of doping metals ceramic membrane biomaterial according to claim 6, it is characterised in that:It is described to mix Miscellaneous metallic cermet films biomaterial improves the service life of artificial organs in artificial organs friction pair in vivo environment.
CN201710710281.3A 2017-08-18 2017-08-18 A kind of doping metals ceramic membrane biomaterial, preparation method and applications Pending CN107587102A (en)

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CN114807845B (en) * 2021-01-28 2024-02-27 山东大学 Titanium copper nitride coating with gradient increasing nitrogen content

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Application publication date: 20180116