CN106967956A - Porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of a kind of maskable harmful ion release - Google Patents
Porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of a kind of maskable harmful ion release Download PDFInfo
- Publication number
- CN106967956A CN106967956A CN201710328710.0A CN201710328710A CN106967956A CN 106967956 A CN106967956 A CN 106967956A CN 201710328710 A CN201710328710 A CN 201710328710A CN 106967956 A CN106967956 A CN 106967956A
- Authority
- CN
- China
- Prior art keywords
- titanium
- hydroxyapatite
- layer
- coating
- porous hydroxyapatite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- 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
-
- 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
- A61L27/32—Phosphorus-containing materials, e.g. apatite
-
- 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
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
- C23C14/0036—Reactive sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3435—Applying energy to the substrate during sputtering
- C23C14/345—Applying energy to the substrate during sputtering using substrate bias
-
- 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
- A61L2400/00—Materials characterised by their function or physical properties
- A61L2400/18—Modification of implant surfaces in order to improve biocompatibility, cell growth, fixation of biomolecules, e.g. plasma treatment
-
- 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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
-
- 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
- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/08—Coatings comprising two or more layers
-
- 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
- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Dermatology (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Transplantation (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Inorganic Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release and purposes, the coating includes titanium prime coat, TiN gradient transitions, TiN layer, alloy/hydroxylapatite gradient transition zone, the porous hydroxyapatite layer set from inside to outside, and the porous hydroxyapatite layer has mesoporous nano structure.Hydroxyapatite layer with mesoporous nano structure can significantly increase the bioactivity of medical metal implant, induce and promote the growth of new bone, accelerate the healing of bone wound；The presence of densification nitridation ti interlayer, can effectively improve the wear resistance and corrosion resistance of medical metal and hinder harmful ion to be discharged to human body, it is to avoid adverse reaction (such as allergy) caused by harmful ion；In addition, coating surface thickness and performance as obtained by the present invention are uniform, coating and substrate combinating strength is high, preparation technology is simple.
Description
Technical field
The present invention relates to a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release and
Preparation method, belongs to Surface Modification of Metallic Biomaterials field.
Background technology
According to statistics, caused by the reasons such as aging population, athletic injury, industrial injury, traffic accident, natural calamity and war
Human body hard tissue damage such as osteoporosis, osteocarcinoma, concellous bonen ecrosis, fracture, Cranial defect disease, cause a large amount of patients to need receiving
Hard tissue repair and replacement operation.Currently, stainless steel, CoCrMo alloys, marmem such as NiTi alloys, pure titanium and titanium are closed
The biomedical metallic material such as gold and magnesium alloy is with its high capacity, and good toughness, easy to process, raw material are cheap and easy to get and good
Biocompatibility and be widely used as hard tissue repairing material.
But a large amount of clinical practice results show that biomedical metallic material is directly exposed under human body fluid environment, exists
It is a large amount of to cause the risk of sclerous tissues's implant failure.It is mainly manifested in：1. stainless steel corrosion-resistant under human body fluid environment, and
Comprising the heavy metal ion such as Cr, Ni in corrosion product, while the erosion of chlorion also increases stainless steel and is broken in body fluid
Risk (Wear, 2000,239 (1):48-58)；2. the cytotoxicity of the element such as Co, Cr, Ni is difficult to solve in CoCrMo alloys
Certainly, clinical practice finds that Co ion concentrations are higher in Urine in Patients, may induce allergic reaction (J Toxicol Clin
Toxicol 1999；37(7):839-844)；3. harmful ion is equally existed in Ti, Ti alloy and NiTi alloy corrosion products
Problem, while its hardness is low, wear no resistance, research shows that fretting wear turns into the main inducing that joint prosthesis is implanted into failure
(Biomaterials,1998,19:1621-1639)；4. magnesium alloy chemical activity is higher, easily occurs under fluid environment rotten
Erosion；5. in composition, tissue and performance with biological bone there are greatest differences in biomedical metallic material, especially be a lack of biological work
Property, cause to only exist mechanical interlock between implant and biological bone, and non-chemical synostosis, it is difficult to form preferable Integrated implant
(Surface&Coatings Technology,2006,200(18):5354-5363).Therefore, in order to overcome medical metal material
Material is in wearability, corrosion-resistant, bioactivity is not enough and the problems such as harmful ion toxic side effect, Chang Qi surfaces prepare biological
Coating (investigation of materials journal, 2000,14 (3):225-233).
Hydroxyapatite (hydroxyapatite, Ca10(PO4)6(OH)2) it is used as the main of biological skeletal tissue and tooth
Part, is typical bioactive coating material.It is consistent with the synthos in bone tissue on composition and structure,
The displacement of the elements such as calcium, phosphorus can be carried out under fluid environment and passes through-OH producing formation of chemical bond synostosis with bone tissue.
Calcium deficiency type HA (d-HA) there are some researches show the Ca/P less than pure ha than 1.67 possesses higher bioactivity (Acta
Biomaterialia,2008,4:1885-1893)；Mesoporous nano structure advantageously in body fluid discharge calcium, phosphorus plasma with
Adhesion, the propagation of osteocyte are induced, promotes the growth of new bone and the Integrated implant of bone tissue and implant.(Surface&
Coatings Technology,2000,131(1-3):181-186).But meso-hole structure necessarily causes hydroxyapatite coating layer
Adhesion reduction between matrix, the body fluid even attack metal matrix by mesoporous gap.For these reasons, it is necessary to
A kind of multi-layer biological coating of function integration is designed, introduces fine and close, wear-resisting between metallic matrix and surface hydroxyl apatite
Corrosion resistant biologically inert layer.Titanium nitride (TiN) is exactly the biologically inert layer of great representational fine and close, wear resistant corrosion resistant.
Because hydroxyapatite with the thermal coefficient of expansion of metallic matrix differs larger, the two can not coordinate in thermal deformation
Unanimously, easily being remained in coat inside internal stress and then causes coating to crack or even come off, macro manifestations be coating with
The adhesion of matrix is low.There are some researches show introduce second in hydroxyapatite and mutually carry out being combined effectively reducing thermal expansion system
Number (functional material, 2007, (38):1808-1812), more preferable match can be reached with metallic matrix；In addition, in hydroxy-apatite
TiN is introduced between stone and metallic matrix and is also beneficial to gradient drop thermal coefficient of expansion, relief of thermal stress gradient, while strengthening Metal Substrate
Body improves wear resistant corrosion resistant energy of the implant under the reciprocation of fluid environment and mechanical force to the bearing capacity of hydroxyapatite
Power, substantially reduces the products such as abrasive dust, harmful ion, can also effectively improve the blood compatibility of metallic matrix, histocompatbility, aobvious
Write reduction cytotoxicity (Rare Metals Materials and engineering, 2007,36 (5):854-861；Surface and Coatings
Technology,2005,200:1014-1017)。
Being presently available for preparing the technique of hydroxyapatite coating layer mainly has sol-gel methods, biomimetic mineralization, electrophoretic deposition
Method, plasma spraying method, magnetron sputtering method and laser cladding etc..Wherein sol-gel methods, biomimetic mineralization method, Hydrothermal Synthesiss etc.
Wet method technology of preparing generally existing bond strength is not high, or even is also difficult to reach required by GB 23101.2-2008 standards
15.0MPa；There is pyrolytic in plasma spraying, the defect such as crackle is more；Laser melting coating prepares coating lack of homogeneity, performance is not
Stable the problems such as.In numerous coat preparing technologies, magnetron sputtering technique has high speed, low temperature two major features, its preparation technology
Relatively simple, bond strength is high, and coating composition is easily controllable, the advantages of can preparing laminated coating.
The content of the invention
The problem of existing for existing medical metal material, can be in medical metal it is an object of the invention to provide one kind
Surface prepares bioactivity height, the maskable harmful ion that abrasion and corrosion resistance is good, biocompatibility is excellent, chemical stability is high
The porous hydroxyapatite of release/nitridation titanium bioactive coating and preparation method thereof.
Technical scheme：To achieve the above object, the technical solution adopted by the present invention is：
A kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release, it is characterised in that：
It is titanium prime coat that the coating includes setting from inside to outside, TiN gradient transitions, TiN layer, alloy/hydroxylapatite gradient transition zone, many
Hole hydroxyapatite layer, the porous hydroxyapatite layer has mesoporous nano structure.
The thickness of the titanium prime coat is 20.0~100.0nm；TiN gradient transitional lay thickness is 0.5~2.0 μm；TiN layer
Thickness be 0.5~3.0 μm；The thickness of alloy/hydroxylapatite gradient transition zone is 0.5~2.0 μm；Porous hydroxyapatite thickness
Spend for 0.2~3.0 μm.
A diameter of 15.0~60.0nm of the mesoporous nano of the porous hydroxyapatite layer.
A kind of preparation method of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release,
Comprise the following steps：
Step one, prepare titanium target first, and prepare hydroxyapatite target；
Step 2, is pre-processed to matrix；
Step 3, pretreated matrix is placed in many target position magnetron sputtering vapor depositing system vacuum sputtering rooms and deposited
Porous hydroxyapatite/nitridation titanium bioactive coating；Wherein, direct current reaction magnetron sputtering technology and radio frequency magnetron is respectively adopted
Sputtering technology depositing titanium nitride gradient transitional lay and porous hydroxyapatite layer；
Step 4, is post-processed to obtained coating.
It is preferred that, in step one, titanium target is used as using high purity titanium；Hydroxyapatite target use size for (10.0~
30.0)×40.0×10.0mm3Fritter be spliced, hydroxyapatite fritter is 0.1~5.0 μm of hydroxy-apatite by particle diameter
Stone powder uses load for 50.0~100.0KN under argon atmosphere, and temperature is pressurize at 1000.0~1500.0 DEG C
It is pressed within 3.0~5.0 hours.
It is preferred that, it is in step 2, the step of substrate pretreated：
The first step, matrix blank is cut into required shape, is then used diamond sand paper to carry out polishing throwing
Light, makes its surface roughness be less than 50.0nm, and distilled water is then used respectively, and alcohol and acetone are respectively cleaned 30.0 minutes；
Second step, cleaned matrix is placed in the KOH alkali lye that concentration is 2.0~5.0mol/L and soaked 24.0 hours,
Continue to clean 40.0 minutes with distilled water ultrasonic wave after base extraction, finally drying 24.0 hours is standby in the environment of 40.0 DEG C
With.
It is preferred that, step 3 is concretely comprised the following steps：
The first step, cleaning matrix and target：Condition is：Vacuum is 1.0~5.0 × 10-5Pa, controls glow discharge air pressure
For 0.6~1.5Pa, substrate bias is -800.0~-1000.0V, utilizes argon plasma sputter clean activated matrix；Close inclined
Voltage source, opens titanium target and hydroxyapatite target power supply and carries out Glow Discharge Cleaning to target material surface；
Second step, titanium deposition prime coat：Condition is：It is 0.5~1.5Pa to control sputtering pressure, and substrate bias is -200.0
~-800.0V, argon flow amount is 50.0~200.0sccm, and DC current is 1.0~5.0A, sputtering sedimentation 2.0~5.0 minutes；
3rd step, depositing TiN gradient transition and TiN layer：Condition is：Continue above-mentioned second step deposition process, with per minute
For interval increase by 1.0~5.0sccm speed be passed through nitrogen into vacuum sputtering room, until nitrogen flow be 10.0~
20.0sccm, and maintain final nitrogen flow to deposit 10.0~20.0 minutes；
4th step, deposited hydroxyl apatite gradient transitional lay：Condition is：It is 0.5~1.5Pa to control sputtering pressure, with every
5.0 minutes interval increase by 100.0~300.0W of radio-frequency power, 0.5~1.0A of reduction DC current, nitrogen flow 3.0~
5.0sccm and substrate bias -100.0~-200.0V, until DC current and nitrogen flow are 0sccm, radio-frequency power is
200.0~600.0W, substrate bias is -50.0~-200.0V；
5th step, deposited porous hydroxyapatite layer：Condition is：Using hydroxyapatite target, radio-frequency sputtering power is
200~600W, sputtering pressure be 0.5~2.0Pa, argon flow amount be 100.0~300.0sccm, substrate bias be -50.0~-
300.0V, sedimentation time is 2.0~6.0 hours.
It is preferred that, in step 4, the post-processing step of coating is：Carried out under atmospheric environment, with 1.0~5.0 DEG C/min
Speed be heated to 400.0~800.0 DEG C and be incubated 3.0~6.0 hours.
It is used for bio-medical metal present invention also offers above-mentioned porous hydroxyapatite/nitridation titanium bioactive coating
Purposes in terms of material shields harmful ion release.
The biomedical metallic material include medical stainless steel, CoCrMo alloys, NiTi alloys, magnesium alloy and pure titanium and
Titanium alloy.
Beneficial effect：The present invention uses the design concept of " biologically inert+bioactivity ", by surface hydroxyl apatite
Fine and close titanium nitride layer lifting wearability, corrosion resistance and the release for hindering metal ion are introduced between metallic matrix, surface is more
Hole hydroxyapatite enhancing bioactivity, and then stability height is designed, adhesion is strong, can promote new bone growth and Integrated implant
Hard implant.Compared with prior art, the beneficial effects of the present invention are：
(1) titanium nitride biologically inert layer is introduced between surface hydroxyl apatite layer and metallic matrix, hydroxyl is effectively alleviated
Coefficient of thermal expansion gradient between base apatite and metallic object matrix, reduces internal stress, enhances adhesion；Fine and close titanium nitride
Layer significantly enhances the corrosion resistance of metallic matrix, the harmful ion discharged by corrosion to human body is effectively reduced, while table
Face porous hydroxyapatite greatly improves the biocompatibility and bioactivity of medical metal matrix, therefore the present invention takes into account
Mechanical properties and biology performance.Hydroxyapatite layer with mesoporous nano structure can significantly increase medical metal implant
Bioactivity, induce and promote the growth of new bone, accelerate the healing of bone wound；The presence of densification nitridation ti interlayer, can have
Effect improves the wear resistance and corrosion resistance of medical metal and hinders harmful ion to be discharged to human body, it is to avoid bad anti-caused by harmful ion
Answer (such as allergy)；
(2) 400.0~600.0 DEG C of heat treatment process can be effectively increased the crystallinity of coating and reduce hydroxyapatite
Hydroxyl, while using the transformation of crystal formation in coating crystallization process, in coating surface formation mesoporous nano, adding the stabilization of coating
Property and bioactivity.
(3) present invention tells that Technological adaptability is good, can be applied to a variety of medical metal material surface enhanced wear resistant corrosion resistants
Performance and biology performance.In addition, present invention process is simple to operate, simple operation, it is easy to accomplish industrialized production.
Brief description of the drawings
The sectional schematic diagram of Fig. 1 coatings prepared by the present invention；
In Fig. 1：1st, matrix；2nd, titanium prime coat；3rd, TiN gradient transitions；4th, TiN layer；5th, alloy/hydroxylapatite gradient transition zone；
6th, porous hydroxyapatite layer.
Fig. 2 schemes for the surface FE-SEM of the prepared coating of the present invention.
The XRD spectrum of Fig. 3 coatings prepared by the present invention.
Fig. 4 is prepared electro-chemical test figure of the coating under calf serum environment of the present invention.
Embodiment
The present invention is further described below in conjunction with the accompanying drawings.
It is as shown in Figure 1 a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release,
It is titanium prime coat 2 that coating includes setting from inside to outside, TiN gradient transitions 3, TiN layer 4, alloy/hydroxylapatite gradient transition zone 5, many
Hole hydroxyapatite layer 6, porous hydroxyapatite layer 6 has mesoporous nano structure.
The coating is deposited on the surface of matrix 1, for shielding harmful ion release.Matrix is biomedical metallic material,
Including medical stainless steel, CoCrMo alloys, NiTi alloys, magnesium alloy and pure titanium or titanium alloy.
It is preferred that, the thickness of titanium prime coat is 20.0~100.0nm；TiN gradient transitional lay thickness is 0.5~2.0 μm；
The thickness of TiN layer is 0.5~3.0 μm；The thickness of alloy/hydroxylapatite gradient transition zone is 0.5~2.0 μm；Porous hydroxyapatite
Thickness degree is 0.2~3.0 μm.A diameter of 15.0~60.0nm of the mesoporous nano of porous hydroxyapatite layer.
The present invention uses magnetron sputtering technique, using surface roughness less than 50.0nm medical metal as matrix, from it is inner to
Outer first layer is titanium prime coat, is then followed successively by biologically inert titanium nitride gradient transitional lay, titanium nitride layer, alloy/hydroxylapatite gradient
Transition zone, surface is porous hydroxyapatite layer.Comprise the following steps that：
Step one, sputtering target material is prepared first：The present invention uses particle diameter for 0.1~5.0 μm of hydroxyapatite powder,
Load is 50.0~100.0KN, and temperature is 1000.0~1500.0 DEG C, and pressurize is pressed under conditions of 3.0~5.0 hours
(10.0~30.0) × 40.0 × 10.0mm3Fritter, protective gas uses argon gas, and the last size according to target position size is spliced
Into the target of required size；
Step 2, is pre-processed to matrix：
(1) matrix blank is cut into required shape, is then used diamond sand paper to carry out sanding and polishing, made
Its surface roughness is less than 50.0nm, and distilled water is then used respectively, and alcohol and acetone are respectively cleaned 30.0 minutes；
(2) cleaned matrix is placed in the KOH alkali lye that concentration is 2.0~5.0mol/L and soaked 24.0 hours, alkali lye
Continue to clean 40.0 minutes with distilled water ultrasonic wave after processing, finally drying 24.0 hours is standby in the environment of 40 DEG C.
Step 3, pretreated matrix is placed in many target position magnetron sputtering vapor depositing system vacuum sputtering rooms and deposited
Porous hydroxyapatite/nitridation titanium bioactive coating；Specifically include：
(1) cleaning matrix and target：Condition is：Vacuum is 1.0~5.0 × 10-5Pa, controls the glow discharge air pressure to be
0.6~1.5Pa, substrate bias is -800.0~-1000.0V, utilizes argon plasma sputter clean activated matrix；Close bias
Power supply, opens titanium target and hydroxyapatite target power supply and carries out Glow Discharge Cleaning to target material surface；
(2) titanium deposition prime coat：Condition is：Control sputtering pressure be 0.5~1.5Pa, substrate bias be -200.0~-
800.0V, argon flow amount is 50.0~200.0sccm, and DC current is 1.0~5.0A, sputtering sedimentation 2.0~5.0 minutes；
(3) depositing TiN gradient transition and TiN layer：Condition is：Continue the deposition process of above-mentioned steps (2), be with per minute
Interval increase by 1.0~5.0sccm speed be passed through nitrogen into vacuum sputtering room, until nitrogen flow be 10.0~
20.0sccm, and maintain final nitrogen flow to deposit 10.0~20.0 minutes；
(4) deposited hydroxyl apatite gradient transitional lay：Condition is：It is 0.5~1.5Pa to control sputtering pressure, with every 5.0 points
Clock interval increases by 100.0~300.0W of radio-frequency power, reduction DC current 0.5~1.0A, 3.0~5.0sccm of nitrogen flow and
Substrate bias -100.0~-200.0V, until DC current and nitrogen flow are 0sccm, radio-frequency power is 200.0~
600.0W, substrate bias is -50.0~-200.0V；
(5) deposited porous hydroxyapatite layer：Condition is：Using hydroxyapatite target, radio-frequency sputtering power is 200~
600W, sputtering pressure be 0.5~2.0Pa, argon flow amount be 100.0~300.0sccm, substrate bias be -50.0~-
300.0V, sedimentation time is 2.0~6.0 hours.
Step 4, is post-processed to obtained coating：Carried out under atmospheric environment, with 1.0~5.0 DEG C/min speed
It is heated to 400.0~800.0 DEG C and is incubated 3.0~6.0 hours；It is final to obtain maskable harmful ion release in matrix surface
Porous hydroxyapatite/nitridation titanium bioactive coating.
With reference to specific implementation case, the present invention is further illustrated, but experimental method and ginseng in case study on implementation
Implementation of the number without limiting the present invention.
Embodiment 1：
Using frequently as bone plate, nail, prosthetic replacement's material Ti-6Al-4V alloys as matrix material and according to
Following steps are carried out：
(1) titanium alloy is cut into 30.0 × 3.0mm of φ3Disk, with 400#, 800#, 1200#, 1500#, 2000# gold
Hard rock sand paper is polished and polished, and is then respectively cleaned after 30.0min and is soaked in distilled water, alcohol and acetone respectively
24.0 hours in 3.0mol/L KOH alkali lye, then proceed to be cleaned with distilled water ultrasonic wave 40.0 minutes, finally at 40.0 DEG C
Under environment dry 24.0 hours it is standby.
(2) cleaning matrix and target, matrix, high-purity Ti target and hydroxyapatite target are installed in vacuum sputtering room,
And it is evacuated down to 5.0 × 10-5Pa, argon gas is passed through into sputtering chamber, and flow is 100.0sccm, and maintenance sputtering chamber ar pressure is
0.6Pa, adjustment matrix location makes it back to target；It is -800V to open grid bias power supply loading bias, and matrix is carried out 20.0 minutes
Argon ion Discharge Cleaning and activation；Grid bias power supply is closed, titanium target and hydroxyapatite target power supply is opened and target material surface is carried out
Glow Discharge Cleaning, titanium target electric current is 2.0A, and hydroxyapatite target power output is 200.0W, and scavenging period is 30.0 minutes.
(3) titanium deposition prime coat, adjustment matrix makes it just to target, opens titanium target and grid bias power supply, and control electric current is
3.0A, bias are -500.0V, and maintenance ar pressure is 0.6Pa, and flow is 100.0sccm, to matrix deposition Ti prime coats, is sunk
The product time is 3.0 minutes.
(4) depositing TiN gradient transition and TiN layer, it is 0.6Pa, total gas to maintain the total pressure in previous step sputtering chamber
Flow is 100.0sccm, while N2Starting flow is 0sccm, increases 2.0sccm with every 1.0 minutes intervals, until increasing to
14.0sccm, control electric current is 3.0A, is biased as -500.0V, and it is that 14.0sccm is deposited 15.0 minutes to maintain nitrogen flow.
(5) deposited hydroxyl apatite gradient transitional lay, it is 0.6Pa to control sputtering pressure, is penetrated with the increase of every 5.0 minutes intervals
Frequency power 100.0W, reduction DC current 1.0A, nitrogen flow 5.0sccm and substrate bias -150.0V, until DC current and
Nitrogen flow is 0, and radio-frequency power is 300.0W, and substrate bias is -50.0V.
(6) deposited hydroxyl apatite layer, the ar pressure closed in nitrogen and titanium target power supply, adjustment sputtering chamber is 0.8Pa,
It is 150.0sccm to control argon flow amount, and hydroxyapatite target sputtering power is 300.0W, is biased as -50.0V, and sedimentation time is
3.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating is post-processed, and under atmospheric environment, is heated to 600.0 DEG C with 3.0 DEG C/min programming rate and is incubated
3.0 hours, then cool to room temperature with the furnace.It is final that maskable harmful ion release is obtained on Ti-6Al-4V alloy substrates surface
Porous hydroxyapatite/nitridation titanium bioactive coating.
Embodiment 2：
Using frequently as bone plate, nail, prosthetic replacement's material 316L stainless steels as matrix material and according to such as
Lower step is carried out：
(1) by 316L stainless steel cuts into 30.0 × 30.0 × 2.0mm3Disk, with 400#, 800#, 1200# diamond
Sand paper is polished and polished, and is then cleaned 30.0 minutes, is finally done in the environment of 40.0 DEG C with distilled water, alcohol and acetone respectively
Dry 24.0 hours standby.
(2) cleaning matrix and target, matrix, high-purity titanium target and hydroxyapatite target are installed in vacuum sputtering room,
And it is evacuated down to 3.0 × 10-5Pa, argon gas is passed through into sputtering chamber, and flow is 120.0sccm, and maintenance sputtering chamber ar pressure is
0.8Pa, adjustment matrix location makes it back to target；It is -1000.0V to open grid bias power supply loading bias, and 30.0 are carried out to matrix
Minute argon ion Discharge Cleaning and activation；Grid bias power supply is closed, titanium target and hydroxyapatite target power supply is opened to target material surface
Glow Discharge Cleaning is carried out, titanium target electric current is 2.0A, and hydroxyapatite target power output is 200.0W, and scavenging period is 30.0 minutes.
(3) titanium deposition prime coat, adjustment matrix makes it just to target, opens titanium target and grid bias power supply, and control electric current is
3.0A, bias are -500.0V, and maintenance ar pressure is 0.8Pa, and flow is 120.0sccm, to matrix deposition titanium prime coat, is sunk
The product time is 3.0 minutes.
(4) depositing TiN gradient transition and TiN layer, it is 0.8Pa to adjust the total pressure in sputtering chamber, and total gas flow is
120.0sccm, while N2Starting flow is 0sccm, increases 3.0sccm with every 1.0 minutes intervals, until increasing to
15.0sccm, control electric current is 3.0A, is biased as -500.0V, and it is that 15.0sccm is deposited 15.0 minutes to maintain nitrogen flow.
(5) deposited hydroxyl apatite gradient transitional lay, it is 1.0Pa to control sputtering pressure, is penetrated with the increase of every 5.0 minutes intervals
Frequency power 150.0W, reduction DC current 1.0A, nitrogen flow 5.0sccm and substrate bias -140.0V, until DC current and
Nitrogen flow is 0, and radio-frequency power is 450.0W, and substrate bias is -80.0V.
(6) deposited hydroxyl apatite layer, the ar pressure closed in nitrogen and titanium target power supply, adjustment sputtering chamber is 1.2Pa,
It is 120.0sccm to control argon flow amount, and hydroxyapatite target sputtering power is 450.0W, is biased as -80.0V, and sedimentation time is
4.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating is post-processed, and under atmospheric environment, is heated to 600.0 DEG C with 3.0 DEG C/min programming rate and is incubated
5.0 hours, then cool to room temperature with the furnace.It is final that many of maskable harmful ion release are obtained on 316L stainless steel bases surface
Hole hydroxyapatite/nitridation titanium bioactive coating.
Embodiment 3：
Using frequently as prosthetic replacement's material CoCrMo alloys are as matrix material and follow the steps below：
(1) CoCrMo alloy substrates are cut into 30.0 × 3.0mm of φ3Disk, with 400#, 800#, 1200#, 1500#
Diamond sand paper is polished and polished, and is soaked in after then cleaning 30.0 minutes with distilled water, alcohol and acetone respectively
24.0 hours in 3.0mol/L KOH alkali lye, then proceed to be cleaned with distilled water ultrasonic wave 40.0 minutes, finally at 40.0 DEG C
Under environment dry 24.0 hours it is standby.
(2) process cleaning target and matrix as described in step 2 in embodiment 2.
(3) titanium deposition prime coat, adjustment matrix makes it just to target, opens titanium target and grid bias power supply, and control electric current is
3.0A, bias are -500.0V, and maintenance ar pressure is 0.8Pa, and flow is 150.0sccm, to matrix deposition titanium prime coat, is sunk
The product time is 2.0 minutes.
(4) total pressure in depositing TiN gradient transition and TiN layer, adjustment sputtering chamber is 0.6Pa, and total gas flow is
150.0sccm, while N2Starting flow is 0sccm, increases 4.0sccm with every 1.0 minutes intervals, until increasing to
20.0sccm, control electric current is 3.0A, is biased as -500.0V, and it is that 20.0sccm is deposited 10.0 minutes to maintain nitrogen flow.
(5) deposited hydroxyl apatite gradient transitional lay, it is 1.2Pa to control sputtering pressure, is penetrated with the increase of every 5.0 minutes intervals
Frequency power 80.0W, reduction DC current 0.8A, nitrogen flow 5.0sccm and substrate bias -100.0V, until DC current and
Nitrogen flow is 0, and radio-frequency power is 320.0W, and substrate bias is -100.0V.
(6) deposited hydroxyl apatite layer, the ar pressure closed in nitrogen and titanium target power supply, adjustment sputtering chamber is 2.0Pa,
It is 150.0sccm to control argon flow amount, and hydroxyapatite target sputtering power is 320.0W, is biased as -100.0V, and sedimentation time is
3.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating is post-processed, and under atmospheric environment, is heated to 600.0 DEG C with 4.0 DEG C/min programming rate and is incubated
4.0 hours, then cool to room temperature with the furnace.It is final that many of maskable harmful ion release are obtained on CoCrMo alloy substrates surface
Hole hydroxyapatite/nitridation titanium bioactive coating.
Fig. 3 is gained porous hydroxyapatite/X of the nitridation titanium bioactive coating after heat treatment in embodiment 1
The characteristic diffraction peak of hydroxyapatite is clearly present in x ray diffraction collection of illustrative plates, figure, after coating is by heat treatment, the crystallinity of coating
It can greatly improve, can effectively reduce the dissolution velocity of coating, its stability and bioactivity will strengthen.
Fig. 4 is that Ti-6Al-4V matrix surfaces deposited porous hydroxyapatite/nitridation titanium bioactive coating is front and rear in ox blood
Electrochemical tests in clear solution, it can be seen that the corrosion potential after surface deposited porous hydroxyapatite/titanium nitride
All just, and corrosion current is minimum for more single titanium nitride coating and Ti-6Al-4V alloy substrate, it is seen that and porous hydroxyapatite/
Titanium nitride coating can reduce the tendency that Ti-6Al-4V alloy substrates corrode, and reduce the corrosion rate of matrix, thus can reduce
The release of the harmful ions such as corrosion product Al, V.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release, it is characterised in that：Institute
State titanium prime coat, TiN gradient transitions, TiN layer that coating includes setting from inside to outside, it is alloy/hydroxylapatite gradient transition zone, porous
Hydroxyapatite layer, the porous hydroxyapatite layer has mesoporous nano structure.
2. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 1
Layer, it is characterised in that：The thickness of the titanium prime coat is 20.0~100.0nm；TiN gradient transitional lay thickness is 0.5~2.0 μ
m；The thickness of TiN layer is 0.5~3.0 μm；The thickness of alloy/hydroxylapatite gradient transition zone is 0.5~2.0 μm；Porous hydroxyapatite phosphorus ash
Rock layers thickness is 0.2~3.0 μm.
3. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 1
Layer, it is characterised in that：A diameter of 15.0~60.0nm of the mesoporous nano of the porous hydroxyapatite layer.
4. a kind of preparation method of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release, its
It is characterised by：Comprise the following steps：
Step one, prepare titanium target first, and prepare hydroxyapatite target；
Step 2, is pre-processed to matrix；
Step 3, deposited porous in many target position magnetron sputtering vapor depositing system vacuum sputtering rooms is placed in by pretreated matrix
Hydroxyapatite/nitridation titanium bioactive coating；Wherein, direct current reaction magnetron sputtering technology and rf magnetron sputtering is respectively adopted
Technology depositing titanium nitride gradient transitional lay and porous hydroxyapatite layer；
Step 4, is post-processed to obtained coating.
5. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 4
The preparation method of layer, it is characterised in that：In step one, titanium target is used as using high purity titanium；Hydroxyapatite target use size for
(10.0~30.0) × 40.0 × 10.0mm3Fritter be spliced, hydroxyapatite fritter is 0.1~5.0 μm by particle diameter
Hydroxyapatite powder uses load for 50.0~100.0KN under argon atmosphere, and temperature is 1000.0~1500.0 DEG C
Lower pressurize is pressed into for 3.0~5.0 hours.
6. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 4
The preparation method of layer, it is characterised in that：It is in step 2, the step of substrate pretreated：
The first step, matrix blank is cut into required shape, is then used diamond sand paper to carry out sanding and polishing, made
Its surface roughness is less than 50.0nm, and distilled water is then used respectively, and alcohol and acetone are respectively cleaned 30.0 minutes；
Second step, cleaned matrix is placed in the KOH alkali lye that concentration is 2.0~5.0mol/L and soaked 24.0 hours, alkali lye
Continue to clean 40.0 minutes with distilled water ultrasonic wave after processing, finally drying 24.0 hours is standby in the environment of 40.0 DEG C.
7. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 4
The preparation method of layer, it is characterised in that：Step 3 is concretely comprised the following steps：
The first step, cleaning matrix and target：Condition is：Vacuum is 1.0~5.0 × 10-5Pa, controls the glow discharge air pressure to be
0.6~1.5Pa, substrate bias is -800.0~-1000.0V, utilizes argon plasma sputter clean activated matrix；Close bias
Power supply, opens titanium target and hydroxyapatite target power supply and carries out Glow Discharge Cleaning to target material surface；
Second step, titanium deposition prime coat：Condition is：Control sputtering pressure be 0.5~1.5Pa, substrate bias be -200.0~-
800.0V, argon flow amount is 50.0~200.0sccm, and DC current is 1.0~5.0A, sputtering sedimentation 2.0~5.0 minutes；
3rd step, depositing TiN gradient transition and TiN layer：Condition is：Continue above-mentioned second step deposition process, with it is per minute be between
Nitrogen is passed through into vacuum sputtering room every the speed for increasing by 1.0~5.0sccm, until nitrogen flow is 10.0~20.0sccm,
And maintain final nitrogen flow to deposit 10.0~20.0 minutes；
4th step, deposited hydroxyl apatite gradient transitional lay：Condition is：It is 0.5~1.5Pa to control sputtering pressure, with every 5.0 points
Clock interval increases by 100.0~300.0W of radio-frequency power, reduction DC current 0.5~1.0A, 3.0~5.0sccm of nitrogen flow and
Substrate bias -100.0~-200.0V, until DC current and nitrogen flow are 0sccm, radio-frequency power is 200.0~
600.0W, substrate bias is -50.0~-200.0V；
5th step, deposited porous hydroxyapatite layer：Condition is：Using hydroxyapatite target, radio-frequency sputtering power is 200~
600W, sputtering pressure be 0.5~2.0Pa, argon flow amount be 100.0~300.0sccm, substrate bias be -50.0~-
300.0V, sedimentation time is 2.0~6.0 hours.
8. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 4
The preparation method of layer, it is characterised in that：In step 4, the post-processing step of coating is：Carried out under atmospheric environment, with 1.0~
5.0 DEG C/min speed is heated to 400.0~800.0 DEG C and is incubated 3.0~6.0 hours.
9. any described porous hydroxyapatite/nitridation titanium bioactive coatings of claim 1-3 are used for bio-medical metal
Material shields harmful ion discharges and improved the purposes in terms of bioactivity.
10. purposes according to claim 9, it is characterised in that：The biomedical metallic material include medical stainless steel,
CoCrMo alloys, NiTi alloys, magnesium alloy and pure titanium or titanium alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328710.0A CN106967956B (en) | 2017-05-11 | 2017-05-11 | A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328710.0A CN106967956B (en) | 2017-05-11 | 2017-05-11 | A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106967956A true CN106967956A (en) | 2017-07-21 |
| CN106967956B CN106967956B (en) | 2019-02-22 |
Family
ID=59331006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710328710.0A Active CN106967956B (en) | 2017-05-11 | 2017-05-11 | A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106967956B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108478859A (en) * | 2018-03-06 | 2018-09-04 | 北京科技大学 | A kind of method that the cold printings of 3D prepare hydroxyapatite-biomedical alloy implant |
| CN110512249A (en) * | 2018-05-22 | 2019-11-29 | 南京理工大学 | The preparation method of titanium carbonitride and carboxy apatite composite coating |
| CN111372533A (en) * | 2017-10-26 | 2020-07-03 | 米尼翁大学 | Dental implant with functional gradient and method for the production thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882377A (en) * | 2014-04-08 | 2014-06-25 | 中国矿业大学 | Method for preparing antibacterial diamond-like carbon/hydroxyapatite gradient multi-element nano coating |
-
2017
- 2017-05-11 CN CN201710328710.0A patent/CN106967956B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103882377A (en) * | 2014-04-08 | 2014-06-25 | 中国矿业大学 | Method for preparing antibacterial diamond-like carbon/hydroxyapatite gradient multi-element nano coating |
Non-Patent Citations (1)
| Title |
|---|
| 贺丹枫: "医用Ti6Al4V合金表面HA及DLC/HA涂层的制备及表征", 《博硕论文-CNKI》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111372533A (en) * | 2017-10-26 | 2020-07-03 | 米尼翁大学 | Dental implant with functional gradient and method for the production thereof |
| CN108478859A (en) * | 2018-03-06 | 2018-09-04 | 北京科技大学 | A kind of method that the cold printings of 3D prepare hydroxyapatite-biomedical alloy implant |
| CN108478859B (en) * | 2018-03-06 | 2020-08-21 | 北京科技大学 | Method for preparing hydroxyapatite-biomedical alloy implant through 3D cold printing |
| CN110512249A (en) * | 2018-05-22 | 2019-11-29 | 南京理工大学 | The preparation method of titanium carbonitride and carboxy apatite composite coating |
| CN110512249B (en) * | 2018-05-22 | 2021-04-27 | 南京理工大学 | Preparation method of titanium carbonitride and hydroxyapatite composite coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106967956B (en) | 2019-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ullah et al. | Mechanical, biological, and antibacterial characteristics of plasma-sprayed (Sr, Zn) substituted hydroxyapatite coating | |
| Roy et al. | Induction plasma sprayed nano hydroxyapatite coatings on titanium for orthopaedic and dental implants | |
| Xue et al. | In vivo evaluation of plasma sprayed hydroxyapatite coatings having different crystallinity | |
| Singh et al. | Characterization and mechanical behaviour of reinforced hydroxyapatite coatings deposited by vacuum plasma spray on SS-316L alloy | |
| CN105397090B (en) | A kind of preparation method of porous nickel-titanium/hydroxyapatite composite material | |
| Qi et al. | Effect of transition layer on the performance of hydroxyapatite/titanium nitride coating developed on Ti-6Al-4V alloy by magnetron sputtering | |
| CN100375640C (en) | Method for treating surface performance of human body hard metal implant | |
| Liu et al. | Synthesis and characterization of porous hydroxyapatite coatings deposited on titanium by flame spraying | |
| CN106967956B (en) | A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release | |
| Cannillo et al. | Thermal and physical characterisation of apatite/wollastonite bioactive glass–ceramics | |
| Mediaswanti et al. | Sputtered hydroxyapatite nanocoatings on novel titanium alloys for biomedical applications | |
| Prashar et al. | Performance of thermally sprayed hydroxyapatite coatings for biomedical implants: a comprehensive review | |
| Suntharavel Muthaiah et al. | Electrophoretic deposition of nanocrystalline calcium phosphate coating for augmenting bioactivity of additively manufactured Ti-6Al-4V | |
| CN103882377A (en) | Method for preparing antibacterial diamond-like carbon/hydroxyapatite gradient multi-element nano coating | |
| CN102580154A (en) | Antifriction and toughening metal/ceramic bionic multilayer-film artificial joint | |
| Sahoo et al. | Synthesis, characterization, and bioactivity of SrTiO3-incorporated titanium coating | |
| Stan et al. | Critical advances in the field of magnetron sputtered bioactive glass thin-films: An analytical review | |
| Oladijo et al. | An Overview of Sputtering Hydroxyapatite for BiomedicalApplication | |
| CN101185773B (en) | Method for preparing bioactivity gradient hard tissue alternate material | |
| Lo et al. | Hydroxyapatite thin films deposited onto uncoated and (Ti, Al, V) N‐coated Ti alloys | |
| CN100577858C (en) | Magnetron sputtering method for preparing HA/YSZ/Ti6Al4V gradient bioactive composite material | |
| CN1221683C (en) | Method and product of sputtering and depositing bioactive gradient hydroxyapatite/Ti layer on Ti alloy surface | |
| Kasuga | Coatings for metallic biomaterials | |
| Singh et al. | An overview of biomedical materials and techniques for better functional performance, life, sustainability and biocompatibility of orthopedic implants | |
| CN108772559B (en) | Bioceramic-based metal composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |