CN105779955B - A kind of hip stem nano surface bioactivity coatings and preparation method thereof - Google Patents

A kind of hip stem nano surface bioactivity coatings and preparation method thereof Download PDF

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CN105779955B
CN105779955B CN201610136729.0A CN201610136729A CN105779955B CN 105779955 B CN105779955 B CN 105779955B CN 201610136729 A CN201610136729 A CN 201610136729A CN 105779955 B CN105779955 B CN 105779955B
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coating
power supply
bioactivity
frequency power
target
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CN105779955A (en
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亓健伟
贺丹枫
王庆良
陈章波
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China University of Mining and Technology CUMT
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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
    • C23C14/22—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
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • 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
    • A61L27/306—Other specific inorganic materials not covered by A61L27/303 - A61L27/32
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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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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract

A kind of hip stem nano surface bioactivity coatings and preparation method thereof.It is characterized in that joint handle surface is made of successively Ti6Al4V matrixes 1, metal Ti layers 2, metal Ti and ceramic of compact mixed layer 3, dense ceramic layers 4, ceramic of compact with BAG/HA/Si mixed layers 5 and BAG/HA/Si multi-element biologics active layer 6.The multifunctional nano gradient composite coating of ingredient consecutive variations is sequentially depositing using non-balance magnetically controlled sputter technology.Coating prepared by the present invention has good bioactivity, biocompatibility and film substrate bond strength, the degradation speed of BAG and the compound controllable coatings of HA is closer to tissue, compact transition layer can effectively prevent the release of harmful metal ion, Si be BAG converted to apatite catalyst, play an important role to initial bone calcification.The present invention can improve the bond strength of prosthesis handle and face coat, and firm chemical bonding is formed with body bone tissue, reduce the release of harmful metal ion, improve the reliability that prosthesis handle uses.

Description

A kind of hip stem nano surface bioactivity coatings and preparation method thereof
Technical field
The present invention relates to a kind of artificial hip joint face coat and preparation method thereof, particularly a kind of hip stem table Face nano-bioactive coating and preparation method thereof.
Background technology
Ti6Al4V alloys are a kind of common artificial joint prosthesis materials, using Ti6Al4V alloys as the surface of joint handle The artificial hip prosthesis of plating nano-bioactive gradient coating.
Since the research of the external biological oxidation object coating of report for the first time in 1931, process for modifying surface and coat type obtain To continuous abundant and development.One side most study, most widely used hydroxyapatite（HA）Coating has good life Object activity and biocompatibility, however when being coated onto Ti6Al4V alloy surfaces, the difference of thermal expansion coefficients of matrix and HA compared with Greatly, therefore coating easily generates peeling, and in addition the degradation speeds of HA in vivo are slower, which also limits it as biological active coating The application of layer；On the other hand, bioactivity glass is as one of biomaterial more early used, possess good bioactivity and Chemical stability, has multicomponent mixture at good mechanical property, and ingredient and structure can adjust in wide range, assigns its difference Performance, controlled micro crystallization processing can effectively improve its intensity, can change glass by adding in alkali and alkaline earth metal ions oxide Glass Network Three-dimensional structure is also widely used so as to change its bioactivity in biomedical sector, and biology is living The difference of thermal expansion coefficients of property glass and Ti6Al4V alloys is smaller, meets the thermal expansion system of Ti6Al4V alloy surface coating materials Number requirement, however its rate of dissolution is too fast, may be completely dissolved when new bone tissue is not formed.
The technology of preparing type of biological coating is various at present, available for preparing the preparation skill of HA and bioactive glass coating Art is also very much.The preparation method of HA coatings mainly has plasma spraying method, sputter coating, pulsed laser deposition, collosol and gel Method, electrophoretic deposition, hydrothermal synthesis method etc..Research finds that coating prepared by plasma spraying easily decomposes at high temperature, and micropore is split The defects of line, is more；Coating prepared by sol-gal process is long placed in easy to crack；It is poor that coated film prepared by electrophoretic deposition-base junction is closed, Coating structure is loose；Sputter coating is for other technologies, and particle energy is in the range of 1-10eV, the film layer prepared Compact structure, ingredient are uniform, and performance is stablized, and deposition velocity is fast, and coating has good adhesive force with matrix, good around plating performance. The technology of preparing of bioactive glass coating is also more, and fusion method, hydro-thermal method and sol-gal process are all common technologies of preparing, Recent domestic also has many scholars to prepare bioactive glass coating using magnetron sputtering technique.Traditional fusion method energy consumption Larger, technique is difficult to accurately control；Coated particle size prepared by hydro-thermal method is excessive, and film quality is poor；Magnetron sputtering technique The coating granule of preparation is tiny, is approached with the stoichiometric ratio of target material composition, and there are atomic levels with the contact interface of matrix Diffusion.Magnetron sputtering is a kind of low-temperature fabrication, is quickly cooled down on target as sputter to substrate, is deposited in the form of amorphous state ；It usually will also result in HA and lacked hydroxyl, this just needs subsequent heat treatment to restore hydroxyl, improves the crystallinity of coating.
Invention content
It is a kind of with shielding plasma diffusing W,Mo ability, superior bio activity and good adhesion the invention aims to provide Hip stem nano surface bioactivity coatings and preparation method thereof, the artificial for solving the manufacture of Ti6Al4V alloys closes Section joint handle combined with bone tissue it is insecure, it is postoperative it is easy lead to the problem of loosen and harmful aluminium, the spilling of vanadium ion.
The object of the present invention is achieved like this：The bioactivity coatings prepare the 1/2-2/ in artificial hip joint handle proximal end The stress-shielding effect with bone tissue firm connection posterior end joint handle is reduced at 3 positions；Total coating thickness is 1-4 μm, coating Ingredient changes from inside to outside in continuous gradient；Artificial hip joint stem face coat is successively by Ti6Al4V matrixes（1）, Ti layers of metal （2）, Ti and ceramic of compact mixed layer（3）, dense ceramic layers（4）, ceramic of compact and bioactivity glass/hydroxyapatite/Si Mixed layer（5）With bioactivity glass/hydroxyapatite/Si multi-element biologic active layers（6）It forms；The thickness of each layer of coating： Ti layers of metal is 100-200nm, and Ti is 50-100nm, dense ceramic layers 200-300nm with ceramic of compact mixed layer, and densification is made pottery Porcelain is more for 100-300nm, bioactivity glass/hydroxyapatite/Si with bioactivity glass/hydroxyapatite/Si mixed layers First bioactive layer is 1-3 μm；The Ti6Al4V Substrate Surface Roughness is less than 0.1 μm.
The dense ceramic layers are one or both of titanium nitride, titanium carbide, titanium carbonitride.
Bioactivity glass/the hydroxyapatite/Si multi-element biologics active layer bioactivity glass required when preparing The mass percent of bioactivity glass/hydroxyapatite is 1 in glass/hydroxyapatite composite target material:4~3:2.
The bioactivity glass is made of following components, and mass percent is：SiO2For 55-65%, CaO 20- 25%、P2O5For 1-5%, Na2O is 7-12%, TiO2For 1-2% and B2O3For 2-5%.
The preparation method of nano-bioactive coating：Artificial hip joint surface polynary nanometer gradient composite coating uses more targets Prepared by the surface-functionalized thin film deposition system of material magnetron sputtering, sputtering process ensures that the ontology vacuum degree of cavity reaches 1-5 × 10- 5Between Pa, target-cardinal distance adjusts in the range of 60-100mm, and matrix frame rotating speed adjusts in the range of 5-10r/min, successively Include the following steps：
Substrate pretreatment：With sand paper sanding and polishing Ti6Al4V matrixes, after surface roughness reaches requirement, it is placed on acetone With 10-15min is respectively washed in ethanol solution；It is 1 that cleaned Ti6Al4V alloys are placed in mass percent:1 sulfuric acid and salt Acid etching activation process is carried out to its surface in the mixed liquor of acid, by mixed liquor heating water bath to 70 DEG C, keeps the temperature 30min, again will Matrix after activation carries out ultrasonic cleaning, is placed on drying for standby in drying box；The mass fraction of the sulfuric acid is 66.3%, The mass fraction of hydrochloric acid is 10.6%；
2. sputter clean：The ontology vacuum degree for being evacuated to sputtering system cavity reaches 1-5 × 10-5Between Pa ranges, lead to Enter argon gas, argon flow amount is maintained between 80-150sccm, and air pressure to be discharged reaches cleaning matrix and cavity between 0.8-3.0Pa Inner wall and activated matrix, the range for adjusting sputtering back bias voltage in-300-- 1200V clean 20min；Back bias voltage is closed, in opening Frequently, radio frequency and DC power supply are respectively washed target, clean Ti targets using intermediate frequency power supply, cleaning condition is：Electric current 0.5-3A, Discharge air pressure 0.8-3.0Pa, argon flow amount 80-120sccm；Ceramic of compact target, cleaning condition are cleaned using radio-frequency power supply For：Power 100-300W, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Si targets are cleaned using DC power supply, clearly Washing process conditions is：Direct current 1-3A, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Hydroxyl is cleaned with radio-frequency power supply Apatite/bioactivity glass composition target, cleaning condition are：Power 100-500W, discharge air pressure 0.8-1.5Pa, argon gas Flow 80-120sccm, sputter clean target material surface pollutant 20-40min；
3. depositing Ti transition zone：Sputtering target material is high-purity titanium target, and Ar ion bombardments, Ar throughputs are 80-150sccm, are adopted With intermediate frequency power supply, discharge air pressure 0.6-1.0Pa, electric current 1-4A, back bias voltage-200-- 500V, sedimentation time 10-30min；
4. deposition compact ceramic coating：Discharge air pressure 0.7-1.0Pa, and argon flow amount 80-120sccm, power is in 150- 400W, bias-150-- 350V deposit 50-100min；Intermediate frequency power supply electric current is reduced to zero with the speed of 0.2A/min, gradually Reduce the Ti contents in coating；Radio-frequency power supply I is opened simultaneously, with one or both of titanium nitride, titanium carbide, titanium carbonitride target As sputtering target material, the power of radio-frequency power supply is improved with the speed of 10W/min, is stepped up TiN, TiC or TiNC in coating Content ensures coating composition from metal Ti to TiN, TiC or TiNC gradient transition；
5. deposit multicomponent biological complex active coating：Discharge air pressure 0.8-1.2Pa, Ar throughput 80-150sccm, keeps Sputtering power is between 100-500W, sputtering bias-voltage is between-100-- 400V, direct current 0.1-1.0A, sedimentation time 6-10h； With the power of the speed reduction radio-frequency power supply I of 20W/min to zero, gradually reduce the content of TiN, TiC or TiNC in coating；With hydroxyl Base apatite/bioactivity glass composition target, Si targets open radio-frequency power supply II and DC power supply deposition apply as sputtering target material Layer, concrete operation step are：Radio-frequency power supply II is opened, the power of radio-frequency power supply II is improved with the speed of 10W/min, is stepped up The content of hydroxyapatite and bioactivity glass in coating, while DC power supply electric current is improved with the speed of 0.01A/min, by Step increases Si element doping amounts in coating, ensures coating composition from TiN, TiC or TiNC to hydroxyapatite/bioactivity glass Glass/Si gradient transitions；
6. coating is heat-treated：The nano-bioactive gradient coating of preparation in resistance furnace is heat-treated, is heat-treated Process conditions are：Steam atmosphere, 3-5 DEG C of heating rate/min, 400-700 DEG C of holding temperature, soaking time 3-6h, after with stove It is cooled to room temperature.
Advantageous effect, as a result of said program, to use non-balance magnetically controlled sputter method depositing coating, in bio-medical It is prepared on metal Ti6Al4V matrixes with good biological activity and biological degradability, the nanometer of certain shielding plasma diffusing W,Mo ability Gradient coating.The design of gradient coating improves chemical binding state, face coat and matrix thermal expansion system between layers The reduction of number difference all plays an important role to the raising of film-film-substrate binding strength.
On the one hand the heat treatment of coating improves the crystallinity of HA, restored the hydroxyl for having great influence to HA bioactivity Base；On the other hand, bioactivity glass after Crystallizing treatment on the basis of original bioactivity is maintained, and improves its power Learn performance.
（1）The design of multicomponent biological complex active coating solve single coating and matrix coefficient of thermal expansion difference it is excessive, The problems such as coating degradation speed and inconsistent human body bone uptake speed；（2）What the three components generation in multi-element coating mutually cooperateed with Effect：The addition of silicon has activated the reaction of osteoblast, improves the bioactivity and bio-compatible of HA and bioactivity glass Property, while bioactivity glass also improves the interface bond strength of HA and Si；（3）Coefficient of thermal expansion is gradually incremented by, and divides gradually Variation, each coating transition interface are that the gradient coating design of the diffusion of atomic level alleviates the internal stress between coating, are changed It has been apt to the adhesive force of coating；(4) design of dense ceramic layers effectively inhibits the release of harmful ion in Ti6Al4V alloys； (5) ingredient of composite coating is harmless.
The artificial hip joint joint handle of Ti6Al4V alloys manufacture is combined insecure, postoperative easy generation with bone tissue Loosen and harmful aluminium, vanadium ion spilling the problem of, reached the purpose of the present invention.
Advantage：The present invention has prepared multi-functional receive using non-balance magnetically controlled sputter technology in Ti6Al4V alloy surfaces Rice complex gradient coating, have shielding plasma diffusing W,Mo ability, superior bio activity and good adhesion etc. series of advantages, have The artificial hip joint stem for solving the manufacture of Ti6Al4V alloys of effect is combined insecure, postoperative easy generation pine with bone tissue The overflow problem of dynamic and harmful aluminium, vanadium ion, improves the reliability that joint handle uses.
Description of the drawings：
Fig. 1 is the structure diagram of the artificial hip joint joint handle superficial film of the present invention.
Fig. 2 is the structure diagram of the Ti6Al4V alloy surface gradient films of the present invention.
In figure,（1）Ti6Al4V matrixes；（2）Ti layers of metal；（3）Ti and ceramic of compact mixed layer；（4）Dense ceramic layers； （5）Ceramic of compact and bioactivity glass/hydroxyapatite/Si mixed layers；（6）Bioactivity glass/hydroxyapatite/Si is more First bioactive layer.
Specific embodiment
The bioactivity coatings are prepared at the 1/2-2/3 positions of artificial hip joint handle proximal end, and reduction is securely tied with bone tissue Close the stress-shielding effect of posterior end joint handle；Total coating thickness is 1-4 μm, and the ingredient of coating becomes from inside to outside in continuous gradient Change, artificial hip joint stem face coat is successively by Ti6Al4V matrixes（1）, Ti layers of metal（2）, Ti and ceramic of compact mixed layer （3）, dense ceramic layers（4）, ceramic of compact and bioactivity glass/hydroxyapatite/Si mixed layers（5）And bioactivity glass Glass/hydroxyapatite/Si multi-element biologic active layers（6）It forms；The thickness of each layer of coating：Ti layers of metal is 100-200nm, Ti It is 50-100nm, dense ceramic layers 200-300nm, ceramic of compact and bioactivity glass/hydroxyl with ceramic of compact mixed layer Apatite/Si mixed layers are 100-300nm, bioactivity glass/hydroxyapatite/Si multi-element biologics active layer is 1-5 μm；Institute The Ti6Al4V Substrate Surface Roughness stated is less than 0.1 μm.
The dense ceramic layers are one or both of titanium nitride, titanium carbide, titanium carbonitride.
Bioactivity glass/the hydroxyapatite/Si multi-element biologics active layer bioactivity glass required when preparing The mass percent of bioactivity glass/hydroxyapatite is 1 in glass/hydroxyapatite composite target material:4~3:2.
The bioactivity glass is made of following components, and mass percent is：SiO2For 55-65%, CaO 20- 25%、P2O5For 1-5%, Na2O is 7-12%, TiO2For 1-2% and B2O3For 2-5%.
The preparation method of nano-bioactive coating：Artificial hip joint surface polynary nanometer gradient composite coating uses more targets Prepared by the surface-functionalized thin film deposition system of material magnetron sputtering, sputtering process ensures that the ontology vacuum degree of cavity reaches 1-5 × 10- 5Between Pa ranges, target-cardinal distance adjusts in the range of 60-100mm, and matrix frame rotating speed adjusts in the range of 5-10r/min, It in turn includes the following steps：
Substrate pretreatment：With sand paper sanding and polishing Ti6Al4V matrixes, after surface roughness reaches requirement, it is placed on acetone With 10-15min is respectively washed in ethanol solution；It is 1 that cleaned Ti6Al4V alloys are placed in mass percent:1 sulfuric acid and salt Acid etching activation process is carried out to its surface in the mixed liquor of acid, by mixed liquor heating water bath to 70 DEG C, keeps the temperature 30min, again will Matrix after activation carries out ultrasonic cleaning, is placed on drying for standby in drying box；The mass fraction of the sulfuric acid is 66.3%, The mass fraction of hydrochloric acid is 10.6%；
2. sputter clean：The ontology vacuum degree for being evacuated to sputtering system cavity reaches 1-5 × 10-5Between Pa ranges, lead to Enter argon gas, argon flow amount is maintained between 80-150sccm, and air pressure to be discharged reaches cleaning matrix and cavity between 0.8-3.0Pa Inner wall and activated matrix, the range for adjusting sputtering back bias voltage in-300-- 1200V clean 20min；Back bias voltage is closed, in opening Frequently, radio frequency and DC power supply are respectively washed target, clean Ti targets using intermediate frequency power supply, cleaning condition is：Electric current 0.5-3A, Discharge air pressure 0.8-3.0Pa, argon flow amount 80-120sccm；Ceramic of compact target, cleaning condition are cleaned using radio-frequency power supply For：Power 100-300W, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Si targets are cleaned using DC power supply, clearly Washing process conditions is：Direct current 1-3A, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Hydroxyl is cleaned with radio-frequency power supply Apatite/bioactivity glass composition target, cleaning condition are：Power 100-500W, discharge air pressure 0.8-1.5Pa, argon gas Flow 80-120sccm.Sputter clean target material surface pollutant 20-40min；
3. depositing Ti transition zone：Sputtering target material is high-purity titanium target, and Ar ion bombardments, Ar throughputs are 80-150sccm, are adopted With intermediate frequency power supply, discharge air pressure 0.6-1.0Pa, electric current 1-4A, back bias voltage-200-- 500V, sedimentation time 10-30min；
4. deposition compact ceramic coating：Discharge air pressure 0.7-1.0Pa, and argon flow amount 80-120sccm, power is in 150- 400W, bias-150-- 350V deposit 50-100min；Intermediate frequency power supply electric current is reduced to zero with the speed of 0.2A/min, gradually Reduce the Ti contents in coating；Radio-frequency power supply I is opened simultaneously, with one or both of titanium nitride, titanium carbide, titanium carbonitride target As sputtering target material, the power of radio-frequency power supply is improved with the speed of 10W/min, is stepped up TiN, TiC or TiNC in coating Content ensures coating composition from metal Ti to TiN, TiC or TiNC gradient transition；
5. deposit multicomponent biological complex active coating：Discharge air pressure 0.8-1.2Pa, Ar throughput 80-150sccm, keeps Sputtering power is between 100-500W, sputtering bias-voltage is between-100-- 400V, direct current 0.1-1.0A, sedimentation time 6-10h； With the power of the speed reduction radio-frequency power supply I of 20W/min to zero, gradually reduce the content of TiN, TiC or TiNC in coating；With hydroxyl Base apatite/bioactivity glass composition target, Si targets open radio-frequency power supply II and DC power supply deposition apply as sputtering target material Layer, concrete operation step are：Radio-frequency power supply II is opened, the power of radio-frequency power supply II is improved with the speed of 10W/min, is stepped up The content of hydroxyapatite and bioactivity glass in coating, while DC power supply electric current is improved with the speed of 0.01A/min, by Step increases Si element doping amounts in coating, ensures coating composition from TiN, TiC or TiNC to hydroxyapatite/bioactivity glass Glass/Si gradient transitions；
6. coating is heat-treated：The nano-bioactive gradient coating of preparation in resistance furnace is heat-treated, is heat-treated Process conditions are：Steam atmosphere, 3-5 DEG C of heating rate/min, 400-700 DEG C of holding temperature, soaking time 3-6h, after with stove It is cooled to room temperature.
It elaborates with reference to embodiment to the present invention：
Embodiment 1：Fig. 1 floating coats are only distributed in the proximal end 1/2-2/3 positions of joint handle.
（1）By the good Ti6Al4V matrixes of sanding and polishing after ultrasonic cleaning, it is 1 to be placed in mass percent:1 sulfuric acid （66.3%）, hydrochloric acid（10.6%）Heating water bath keeps the temperature 30min acid etching activation process, ultrasonic cleaning acid to 70 DEG C in mixed liquor Matrix after erosion is placed on drying for standby in drying box；
（2）Adjustment target-cardinal distance is 60mm, and the ontology vacuum degree for being evacuated to cavity reaches 2 × 10-5Pa is passed through argon gas, argon Throughput is 120sccm, and electric discharge air pressure is 1.0Pa, and grid bias power supply is adjusted to -500V, cleans matrix surface and cavity inner wall pollution Object and activating surface 15min；
（3）Adjustment argon flow amount is 100sccm, and electric discharge air pressure remains unchanged, and closes grid bias power supply, adjusts intermediate frequency power supply electricity Flow 1A cleanings titanium target, DC power supply electric current 2A cleanings silicon target, I power 200W cleaning ceramics target of radio-frequency power supply, II work(of radio-frequency power supply Rate 300W cleans hydroxyapatite/bioactivity glass composition target, cleaning target material surface pollutant 20min；
（4）Sputtering target material is titanium target, using intermediate frequency power supply, adjusts the air pressure 0.8Pa that discharges, argon flow amount 100sccm, electric current 1A, back bias voltage -200V, depositing Ti layer 25min；
（5）Using titanium nitride as sputtering target material, adjustment electric discharge air pressure 0.8Pa, argon flow amount 100sccm, with 0.2A/min Speed reduce intermediate frequency power supply electric current to 0, gradually reduce the Ti contents in coating, radio-frequency power supply I improved with the speed of 10W/min Power to 200W, be stepped up the content of TiN in coating, slowly adjust negative bias and be depressed into -250V, ensure coating composition by metal Ti is to TiN gradient transitions, deposition compact ceramic coating 1h；
（6）Using silicon target and bioactivity glass/hydroxyapatite composition target as sputtering target material, bioactivity in composition target The mass percent of glass/hydroxyapatite is 3:5, the component of bioactivity glass is SiO2(57%)、CaO（25%）、P2O5 （2%）、Na2O（10%）、TiO2（1.5%）、B2O3（4.5%）.Adjustment electric discharge air pressure 1.0Pa, argon flow amount 120sccm, with 20W/ The speed of min reduces the power of radio-frequency power supply I to 0, gradually reduces the content of TiN in coating, is penetrated with the speed raising of 10W/min The power of frequency power II is stepped up the content of HA and bioactivity glass in coating, is carried with the speed of 0.01A/min to 300W High DC power supply electric current is stepped up element silicon doping in coating, slowly adjusts negative bias and be depressed into -200V, ensure to apply to 0.2A For composition of layer from TiN to hydroxyapatite/bioactivity glass/Si gradient transitions, deposition mixes Si bioactivity composite coatings 8h；
（7）The nano-bioactive gradient coating of preparation is heat-treated in resistance furnace under steam atmosphere, is heated up 3 DEG C/min of rate, 600 DEG C, soaking time 5h of holding temperature, after cool to room temperature with the furnace, finally in Ti6Al4V matrix surface systems The biologically active nanometer gradient coating of standby high bond strength.
Embodiment 2：
（1）The good Ti6Al4V matrixes of sanding and polishing are placed on each 15min of ultrasonic cleaning in acetone and alcohol, are placed on dry Drying for standby in dry case；
（2）Adjustment target-cardinal distance is 80mm, is evacuated to cavity body vacuum degree and reaches 1 × 10-5Pa is passed through argon gas, argon gas Flow is 100sccm, and electric discharge air pressure is 1.0Pa, and grid bias power supply is adjusted to -800V, cleans matrix surface and cavity inner wall pollutant And activating surface 15min；
（3）Adjustment electric discharge air pressure is 0.8Pa, and argon flow amount remains unchanged, and closes grid bias power supply, adjusts intermediate frequency power supply electric current 1A cleanings titanium target, DC power supply electric current 1A cleanings silicon target, I power 300W cleaning ceramics target of radio-frequency power supply, II power of radio-frequency power supply 300W cleans HA and bioactivity glass composition target, cleaning target material surface pollutant 25min；
（4）Sputtering target material is titanium target, using intermediate frequency power supply, adjusts the air pressure 1.0Pa that discharges, argon flow amount 120sccm, electric current 1.2A, back bias voltage -200V, depositing Ti layer 20min；
（5）Using titanium carbide as sputtering target material, adjustment electric discharge air pressure is 1.0Pa, argon flow amount 80sccm, with 0.2A/min Speed reduce intermediate frequency power supply electric current to 0, gradually reduce the Ti contents in coating, radio-frequency power supply I improved with the speed of 10W/min Power to 250W, be stepped up the content of TiC in coating, slowly adjust negative bias and be depressed into -300V, ensure coating composition by metal Ti is to TiC gradient transitions, deposition compact ceramic coating 50min；
（6）Using silicon target and bioactivity glass/hydroxyapatite composition target as sputtering target material, bioactivity in composition target The mass percent of glass/hydroxyapatite is 4:5, the component of bioactivity glass is SiO2(57%)、CaO（25%）、P2O5 （2.5%）、Na2O（10%）、TiO2（1.5%）、B2O3（4%）.Adjustment discharges air pressure for 1.2Pa, argon flow amount 100sccm, with The speed of 20W/min reduces the power of radio-frequency power supply I to 0, gradually reduces the content of TiC in coating, is carried with the speed of 10W/min The power of frequency power II is shot high to 250W, the content of HA and bioactivity glass in coating is stepped up, with the speed of 0.01A/min Degree improves DC power supply electric current to 0.3A, is stepped up element silicon doping in coating, slowly adjusts negative bias and be depressed into -300V, protect Coating composition is demonstrate,proved from TiC to hydroxyapatite/bioactivity glass/Si gradient transitions, deposition mixes Si bioactivity coatings 7h；
（7）The nano-bioactive gradient coating of preparation is heat-treated in resistance furnace under steam atmosphere, is heated up 3 DEG C/min of rate, 700 DEG C, soaking time 4h of holding temperature, after cool to room temperature with the furnace, finally in Ti6Al4V matrix surface systems The biologically active nanometer gradient coating of standby high bond strength.
Embodiment 3：
（1）By the good Ti6Al4V matrixes of sanding and polishing after ultrasonic cleaning, it is 1 to be placed in mass percent:1 sulfuric acid （66.3%）, hydrochloric acid（10.6%）Acid etching activation process 1h at room temperature in mixed liquor, the matrix after ultrasonic cleaning acid etching, is placed on dry Drying for standby in dry case；
（2）Adjustment target-cardinal distance is 100mm, and the ontology vacuum degree for being evacuated to cavity reaches 3 × 10-5Pa is passed through argon gas, Argon flow amount is 150sccm, and electric discharge air pressure is 0.8Pa, and grid bias power supply is adjusted to -300V, cleans matrix surface and cavity inner wall is dirty Contaminate object and activating surface 20min；
（3）Adjustment electric discharge air pressure is 1.2Pa, argon flow amount 120sccm, closes grid bias power supply, adjustment intermediate frequency power supply electricity Flow 1.5A cleanings titanium target, DC power supply electric current 2A cleanings silicon target, I power 300W cleaning ceramics target of radio-frequency power supply, radio-frequency power supply II Power 350W cleans HA and bioactivity glass composition target, cleaning target material surface pollutant 15min；
（4）Sputtering target material is titanium target, and using intermediate frequency power supply, adjustment discharges air pressure for 1.0Pa, argon flow amount 100sccm, electricity Flow 1.2A, back bias voltage -300V, depositing Ti layer 20min；
（5）Using titanium carbonitride as sputtering target material, adjustment electric discharge air pressure is 0.8Pa, argon flow amount 120sccm, with 0.2A/ The speed of min reduces intermediate frequency power supply electric current to 0, gradually reduces the Ti contents in coating, radio frequency electrical is improved with the speed of 10W/min The power in source I is stepped up the content of TiNC in coating to 300W, slowly adjusts negative bias and is depressed into -200V, ensure coating composition by Metal Ti is to TiNC gradient transitions, deposition compact ceramic coating 1h；
（6）Using silicon target and bioactivity glass/hydroxyapatite composition target as sputtering target material, bioactivity in composition target The mass percent of glass/hydroxyapatite is 3:5, the component of bioactivity glass is SiO2(57%)、CaO（25%）、P2O5 （2%）、Na2O（10%）、TiO2（1.5%）、B2O3（4.5%）.Adjustment discharges air pressure for 0.8Pa, argon flow amount 120sccm, with The speed of 20W/min reduces the power of radio-frequency power supply I to 0, and step reduces the content of TiNC in coating, is carried with the speed of 10W/min The power of frequency power II is shot high to 300W, the content of HA and bioactivity glass in coating is stepped up, with the speed of 0.01A/min Degree improves DC power supply electric current to 0.2A, is stepped up element silicon doping in coating, slowly adjusts negative bias and be depressed into -350V, protect Coating composition is demonstrate,proved from TiNC to hydroxyapatite/bioactivity glass/Si gradient transitions, deposition mixes Si bioactivity coatings 8h；
（7）The nano-bioactive gradient coating of preparation is heat-treated in resistance furnace under steam atmosphere, is heated up 5 DEG C/min of rate, 500 DEG C, soaking time 7h of holding temperature, after cool to room temperature with the furnace, finally in Ti6Al4V matrix surface systems The biologically active nanometer gradient coating of standby high bond strength.

Claims (5)

1. a kind of hip stem nano surface bioactivity coatings, it is characterized in that：The bioactivity coatings are prepared artificial The stress-shielding effect with bone tissue firm connection posterior end joint handle is reduced at the 1/2-2/3 positions of hip joint stalk proximal end；Coating Overall thickness is 1-4 μm, and the ingredient of coating changes from inside to outside in continuous gradient, artificial hip joint stem face coat successively by Ti6Al4V matrixes (1), metal Ti layers (2), Ti and ceramic of compact mixed layer (3), dense ceramic layers (4), ceramic of compact and biology Activity glass/hydroxyapatite/Si mixed layers (5) and bioactivity glass/hydroxyapatite/Si multi-element biologics active layer (6) It forms；The thickness of each layer of coating：Ti layers of metal is 100-200nm, and Ti is 50-100nm with ceramic of compact mixed layer, and densification is made pottery Enamel coating is that 200-300nm, ceramic of compact and bioactivity glass/hydroxyapatite/Si mixed layers are living for 100-300nm, biology Property glass/hydroxyapatite/Si multi-element biologics active layer be 1-3 μm；The Ti6Al4V Substrate Surface Roughness is less than 0.1 μ m。
2. a kind of hip stem nano surface bioactivity coatings according to claim 1, it is characterized in that：Described Dense ceramic layers are one or both of titanium nitride, titanium carbide, titanium carbonitride.
3. a kind of hip stem nano surface bioactivity coatings according to claim 1, it is characterized in that：Described Bioactivity glass/hydroxyapatite/Si multi-element biologics active layer bioactivity glass/hydroxyapatite required when preparing is multiple The mass percent for closing bioactivity glass/hydroxyapatite in target is 1:4~3:2.
4. a kind of hip stem nano surface bioactivity coatings according to claim 1, it is characterized in that：Described Bioactivity glass is made of following components, and mass percent is：SiO2For 55-65%, CaO 20-25%, P2O5For 1-5%, Na2O is 7-12%, TiO2For 1-2% and B2O3For 2-5%.
5. a kind of preparation method of hip stem nano surface bioactivity coatings according to claim 1, special Sign is：The preparation method of nano-bioactive coating：Artificial hip joint surface polynary nanometer gradient composite coating uses more targets Prepared by the surface-functionalized thin film deposition system of magnetron sputtering, sputtering process ensures that the ontology vacuum degree of cavity reaches 1-5 × 10-5Pa Between, target-cardinal distance adjusts in the range of 60-100mm, and matrix frame rotating speed adjusts in the range of 5-10r/min, includes successively Following steps：
1. substrate pretreatment：With sand paper sanding and polishing Ti6Al4V matrixes, after surface roughness reaches requirement, it is placed on acetone and second 10-15min is respectively washed in alcoholic solution；It is 1 that cleaned Ti6Al4V alloys are placed in mass percent:1 sulfuric acid and hydrochloric acid Acid etching activation process is carried out to its surface in mixed liquor, by mixed liquor heating water bath to 70 DEG C, keeps the temperature 30min, it again will activation Matrix afterwards carries out ultrasonic cleaning, is placed on drying for standby in drying box；The mass fraction of the sulfuric acid is 66.3%, hydrochloric acid Mass fraction be 10.6%；
2. sputter clean：The ontology vacuum degree for being evacuated to sputtering system cavity reaches 1-5 × 10-5Between Pa ranges, it is passed through argon Gas, argon flow amount are maintained between 80-150sccm, and air pressure to be discharged reaches cleaning matrix and cavity inner wall between 0.8-3.0Pa And activated matrix, the range for adjusting sputtering back bias voltage in-300-- 1200V clean 20min；Back bias voltage is closed, intermediate frequency is opened, penetrates Frequency and DC power supply are respectively washed target, clean Ti targets using intermediate frequency power supply, cleaning condition is：Electric current 0.5-3A, electric discharge Air pressure 0.8-3.0Pa, argon flow amount 80-120sccm；Ceramic of compact target is cleaned using radio-frequency power supply, cleaning condition is：Work( Rate 100-300W, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Si targets, cleaning are cleaned using DC power supply Condition is：Direct current 1-3A, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm；Hydroxy-apatite is cleaned with radio-frequency power supply Stone/bioactivity glass composition target, cleaning condition are：Power 100-500W, discharge air pressure 0.8-1.5Pa, argon flow amount 80-120sccm, sputter clean target material surface pollutant 20-40min；
3. depositing Ti transition zone：Sputtering target material is high-purity titanium target, and Ar ion bombardments, Ar throughputs are 80-150sccm, in Frequency power, discharge air pressure 0.6-1.0Pa, electric current 1-4A, back bias voltage-200-- 500V, sedimentation time 10-30min；
4. deposition compact ceramic coating：Discharge air pressure 0.7-1.0Pa, argon flow amount 80-120sccm, power 150-400W, partially - 150-- 350V is pressed, deposits 50-100min；Intermediate frequency power supply electric current is reduced to zero with the speed of 0.2A/min, gradually reduces coating In Ti contents；Radio-frequency power supply I is opened simultaneously, using one or both of titanium nitride, titanium carbide, titanium carbonitride target as sputtering Target improves the power of radio-frequency power supply with the speed of 10W/min, is stepped up the content of TiN, TiC or TiNC in coating, ensures Coating composition is from metal Ti to TiN, TiC or TiNC gradient transition；
5. deposit multicomponent biological complex active coating：Discharge air pressure 0.8-1.2Pa, Ar throughput 80-150sccm, keeps sputtering Power is between 100-500W, sputtering bias-voltage is between-100-- 400V, direct current 0.1-1.0A, sedimentation time 6-10h；With The speed of 20W/min reduces the power of radio-frequency power supply I to zero, gradually reduces the content of TiN, TiC or TiNC in coating；With hydroxyl Apatite/bioactivity glass composition target, Si targets open radio-frequency power supply II and DC power supply depositing coating as sputtering target material, Concrete operation step is：Radio-frequency power supply II is opened, the power of radio-frequency power supply II is improved with the speed of 10W/min, is stepped up applying The content of hydroxyapatite and bioactivity glass in layer, while DC power supply electric current is improved with the speed of 0.01A/min, gradually Increase coating in Si element doping amounts, ensure coating composition from TiN, TiC or TiNC to hydroxyapatite/bioactivity glass/ Si gradient transitions；
6. coating is heat-treated：The nano-bioactive gradient coating of preparation is heat-treated in resistance furnace, heat treatment process Condition is：Steam atmosphere, 3-5 DEG C of heating rate/min, 400-700 DEG C of holding temperature, soaking time 3-6h, rear furnace cooling To room temperature.
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