CN106967956B - A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release - Google Patents
A kind of porous hydroxyapatite/nitridation the titanium bioactive coating and purposes of maskable harmful ion release Download PDFInfo
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—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
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- A61L27/28—Materials for coating prostheses
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- A61L27/28—Materials for coating prostheses
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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
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- 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
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- 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
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- A61L2420/00—Materials or methods for coatings medical devices
- A61L2420/02—Methods for coating medical devices
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- A61L2420/08—Coatings comprising two or more layers
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- A61L2430/00—Materials or treatment for tissue regeneration
- A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants
Abstract
The invention discloses the porous hydroxyapatite/nitridation titanium bioactive coatings and purposes of a kind of maskable harmful ion release, the coating includes the titanium prime coat being arranged from inside to outside, TiN gradient transition, TiN layer, alloy/hydroxylapatite gradient transition zone, porous hydroxyapatite layer, 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 harmful ion is hindered to discharge to human body, adverse reaction (such as allergy) caused by avoiding because of harmful ion；In addition, gained coating surface thickness and performance are uniform through the invention, coating and substrate combinating strength are high, preparation process 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 technique
According to statistics, caused by because of reasons such as aging of population, athletic injury, industrial injury, traffic accident, natural calamity and wars
Human body hard tissue damage such as osteoporosis, osteocarcinoma, concellous bonen ecrosis, fracture, bone defect disease, cause a large amount of patients to need to receive
Hard tissue repair and replacement operation.Currently, stainless steel, CoCrMo alloy, marmem such as NiTi alloy, pure titanium and titanium close
The biomedical metallic materials such as gold and magnesium alloy are with its bearing capacity height, and good toughness, easy to process, raw material is cheap and easy to get and good
Biocompatibility and be widely used as hard tissue repairing material.
However a large amount of clinical practices the result shows that, biomedical metallic material is directly exposed under human body fluid environment, exists
The risk for largely causing sclerous tissues' implant to fail.It is mainly manifested in: 1. stainless steel poor corrosion resistance under human body fluid environment, and
Comprising the heavy metal ion such as Cr, Ni in corrosion product, while the erosion of chloride ion also increases stainless steel and is broken in body fluid
Risk (Wear, 2000,239 (1): 48-58)；2. the cytotoxicity of the elements such as Co, Cr, Ni is difficult to solve in CoCrMo alloy
Certainly, Co ion concentration is higher in clinical practice discovery Urine in Patients, may induce allergic reaction (J Toxicol Clin
Toxicol 1999；37(7):839-844)；3. equally existing harmful ion in Ti, Ti alloy and NiTi alloy corrosion product
Problem, while its hardness is low, wears no resistance, research shows that fretting wear becomes the main inducing of joint prosthesis implantation failure
(Biomaterials,1998,19:1621-1639)；4. magnesium alloy chemical activity is higher, corruption is easy to happen under fluid environment
Erosion；5. there are greatest differences with biological bone in ingredient, tissue and performance for biomedical metallic material, it is especially a lack of biological work
Property causes between implant and biological bone there is only mechanical interlock, and non-chemical synostosis, it is difficult to form ideal Integrated implant
(Surface&Coatings Technology,2006,200(18):5354-5363).Therefore, in order to overcome medical metal material
Material wearability, corrosion-resistant, bioactivity is insufficient and the toxic side effect of harmful ion the problems such as, biology is often prepared on its surface
Coating (investigation of materials journal, 2000,14 (3): 225-233).
Hydroxyapatite (hydroxyapatite, Ca10(PO4)6(OH)2) as the main of biological skeletal tissue and tooth
Component part is typical bioactive coating material.It is consistent with the synthos in bone tissue on ingredient and structure,
It is able to carry out the displacement of the elements such as calcium, phosphorus under fluid environment and formation of chemical bond synostosis is generated by-OH and bone tissue.
Some researches show that calcium deficiency type HA (d-HA) of the Ca/P than 1.67 lower than pure ha to possess higher bioactivity (Acta
Biomaterialia,2008,4:1885-1893)；Mesoporous nano structure be more conducive to body fluid discharge calcium, phosphorus plasma with
Adherency, the proliferation for inducing osteocyte, promote the growth of new bone and the Integrated implant of bone tissue and implant.(Surface&
Coatings Technology,2000,131(1-3):181-186).However meso-hole structure necessarily leads to hydroxyapatite coating layer
Binding force between matrix reduces, and body fluid even passes through mesoporous gap attack metal matrix.For these reasons, it is necessary to
The multi-layer biological coating for designing a kind of function integration introduces fine and close, wear-resisting between metallic matrix and surface hydroxyl apatite
Corrosion resistant biologically inert layer.Titanium nitride (TiN) is exactly great representative fine and close, wear resistant corrosion resistant biologically inert layer.
Since hydroxyapatite differs larger with the thermal expansion coefficient of metallic matrix, the two can not be coordinated in thermal deformation
Unanimously, being easy to remain in coat inside internal stress and then causes coating to crack or even fall off, macro manifestations be coating with
The binding force of matrix is low.Some researches show that introduce compound can effectively reduce of the second phase progress in hydroxyapatite and thermally expand system
Number (functional material, 2007, (38): 1808-1812), can reach better matching with metallic matrix；In addition, in hydroxy-apatite
TiN is introduced between stone and metallic matrix and is also beneficial to gradient drop thermal expansion coefficient, relief of thermal stress gradient, while enhancing 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, show
Writing reduces cytotoxicity (Rare Metals Materials and engineering, 2007,36 (5): 854-861；Surface and Coatings
Technology,2005,200:1014-1017)。
The technique for being presently available for preparing hydroxyapatite coating layer mainly has sol-gel method, biomimetic mineralization, electrophoretic deposition
Method, plasma spraying method, magnetron sputtering method and laser cladding etc..Wherein sol-gel method, biomimetic mineralization method, hydrothermal synthesis etc.
The generally existing bond strength of wet process technology of preparing is not high, or even is also difficult to required by reaching GB 23101.2-2008 standard
15.0MPa；Plasma spraying is there are pyrolytic, the defects of crackle is more；Laser melting coating prepares coating uniformity is poor, and performance is not
The problems such as stablizing.In numerous coat preparing technologies, magnetron sputtering technique has high speed, low temperature two major features, preparation process
The advantages that relatively simple, bond strength is high, and coating composition is easily controllable, can prepare laminated coating.
Summary of the invention
Existing medical metal material there are aiming at the problem that, the purpose of the present invention is to provide one kind can be in medical metal
Surface prepares the maskable harmful ion that bioactivity is high, 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 solution: to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release, it is characterised in that:
The coating includes the titanium prime coat being arranged from inside to outside, TiN gradient transition, TiN layer, alloy/hydroxylapatite gradient transition zone, more
Hole hydroxyapatite layer, the porous hydroxyapatite layer have mesoporous nano structure.
The titanium prime coat with a thickness of 20.0~100.0nm；TiN gradient transitional lay is with a thickness of 0.5~2.0 μm；TiN layer
With a thickness of 0.5~3.0 μm；Alloy/hydroxylapatite gradient transition zone with a thickness of 0.5~2.0 μm；Porous hydroxyapatite thickness
Degree is 0.2~3.0 μm.
The diameter of the mesoporous nano of the porous hydroxyapatite layer is 15.0~60.0nm.
A kind of porous hydroxyapatite/nitridation titanium bioactive coating preparation method of maskable harmful ion release,
The following steps are included:
Step 1, first preparation titanium target, and prepare hydroxyapatite target；
Step 2 pre-processes matrix；
Pretreated matrix is placed in more target position magnetron sputtering vapor depositing system vacuum sputterings room and deposits by step 3
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 post-processes obtained coating.
Preferably, in step 1, using high purity titanium as titanium target；Hydroxyapatite target use having a size of (10.0~
30.0)×40.0×10.0mm3Fritter be spliced, hydroxyapatite fritter is 0.1~5.0 μm of hydroxy-apatite by partial size
Stone powder uses load for 50.0~100.0KN under argon atmosphere, and temperature is pressure maintaining at 1000.0~1500.0 DEG C
It is pressed within 3.0~5.0 hours.
Preferably, in step 2, the step of substrate pretreated are as follows:
Matrix blank is cut into required shape, diamond sand paper is then used to carry out polishing throwing by the first step
Light makes its surface roughness be less than 50.0nm, then uses distilled water respectively, alcohol and acetone respectively clean 30.0 minutes；
Cleaned matrix is placed in the KOH lye that concentration is 2.0~5.0mol/L and impregnates 24.0 hours by second step,
Continue after base extraction with distilled water ultrasonic cleaning 40.0 minutes, finally in the environment of 40.0 DEG C dry 24.0 hours it is standby
With.
Preferably, the specific steps of step 3 are as follows:
The first step cleans matrix and target: condition are as follows: vacuum degree 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；It closes inclined
Voltage source opens titanium target and hydroxyapatite target power supply and carries out Glow Discharge Cleaning to target material surface；
Second step deposits titanium prime coat: condition are as follows: control sputtering pressure is 0.5~1.5Pa, and substrate bias is -200.0
~-800.0V, argon flow be 50.0~200.0sccm, DC current be 1.0~5.0A, sputtering sedimentation 2.0~5.0 minutes；
Third step, depositing TiN gradient transition and TiN layer: condition are as follows: 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 final nitrogen flow is maintained to deposit 10.0~20.0 minutes；
4th step deposits alloy/hydroxylapatite gradient transition zone: condition are as follows: control sputtering pressure is 0.5~1.5Pa, with every
5.0 minutes interval increase by 100.0~300.0W of radio-frequency power, reduction by 0.5~1.0A of 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 are -50.0~-200.0V；
5th step, deposited porous hydroxyapatite layer: condition are as follows: use hydroxyapatite target, rf sputtering power is
200~600W, sputtering pressure be 0.5~2.0Pa, argon flow be 100.0~300.0sccm, substrate bias be -50.0~-
300.0V, sedimentation time are 2.0~6.0 hours.
Preferably, in step 4, the post-processing step of coating are as follows: carried out under atmospheric environment, with 1.0~5.0 DEG C/min
Speed be heated to 400.0~800.0 DEG C and keep the temperature 3.0~6.0 hours.
The present invention also provides above-mentioned porous hydroxyapatite/nitridation titanium bioactive coatings to be used for bio-medical metal
The purposes of material shields harmful ion release aspect.
The biomedical metallic material include medical stainless steel, CoCrMo alloy, NiTi alloy, magnesium alloy and pure titanium and
Titanium alloy.
The utility model has the advantages that design concept of the present invention using " biologically inert+bioactivity ", by surface hydroxyl apatite
It is more that fine and close titanium nitride layer promotion wearability, corrosion resistance and the release for hindering metal ion, surface are introduced between metallic matrix
Hole hydroxyapatite enhances bioactivity, and then designs stability height, and binding force 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, and hydroxyl has been effectively relieved
Coefficient of thermal expansion gradient between base apatite and metallic object matrix, reduces internal stress, enhances binding force；Fine and close titanium nitride
Layer significantly enhances the corrosion resistance of metallic matrix, and the harmful ion discharged due to corrosion to human body, while table is effectively reduced
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 harmful ion is hindered to discharge to human body, bad anti-caused by avoiding because of harmful ion
Answer (such as allergy)；
(2) 400.0~600.0 DEG C of heat treatment process can effectively increase the crystallinity of coating and restore hydroxyapatite
Hydroxyl, while using the transformation of crystal form in coating crystallization process, mesoporous nano is formed in coating surface, increases the stabilization of coating
Property and bioactivity.
(3) the told Technological adaptability of the present invention 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 easy to operate, it is convenient to operate, it is easy to accomplish industrialized production.
Detailed description of the invention
Fig. 1 is the sectional schematic diagram of coating prepared by the present invention；
In Fig. 1: 1, matrix；2, titanium prime coat；3, TiN gradient transition；4, TiN layer；5, alloy/hydroxylapatite gradient transition zone；
6, porous hydroxyapatite layer.
Fig. 2 is the surface FE-SEM figure of coating prepared by the present invention.
Fig. 3 is the XRD spectrum of coating prepared by the present invention.
Fig. 4 is electro-chemical test figure of the coating under calf serum environment prepared by the present invention.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawing.
It is as shown in Figure 1 a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release,
Coating includes the titanium prime coat 2 being arranged from inside to outside, TiN gradient transition 3, TiN layer 4, alloy/hydroxylapatite gradient transition zone 5, more
Hole hydroxyapatite layer 6, porous hydroxyapatite layer 6 have 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 alloy, NiTi alloy, magnesium alloy and pure titanium or titanium alloy.
Preferably, titanium prime coat with a thickness of 20.0~100.0nm；TiN gradient transitional lay is with a thickness of 0.5~2.0 μm；
TiN layer with a thickness of 0.5~3.0 μm；Alloy/hydroxylapatite gradient transition zone with a thickness of 0.5~2.0 μm；Porous hydroxyapatite
Layer is with a thickness of 0.2~3.0 μm.The diameter of the mesoporous nano of porous hydroxyapatite layer is 15.0~60.0nm.
The present invention use magnetron sputtering technique, using surface roughness lower 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 are porous hydroxyapatite layer.Specific step is as follows:
Step 1 prepares sputtering target material first: the present invention uses partial size 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 pressure maintaining 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
At the target of required size；
Step 2 pre-processes matrix:
(1) matrix blank is cut into required shape, is then used diamond sand paper to carry out sanding and polishing, is made
Its surface roughness is less than 50.0nm, then uses distilled water respectively, alcohol and acetone respectively clean 30.0 minutes；
(2) cleaned matrix is placed in the KOH lye that concentration is 2.0~5.0mol/L and is impregnated 24.0 hours, lye
Continue after processing with distilled water ultrasonic cleaning 40.0 minutes, finally in the environment of 40 DEG C dry 24.0 hours it is spare.
Pretreated matrix is placed in more target position magnetron sputtering vapor depositing system vacuum sputterings room and deposits by step 3
Porous hydroxyapatite/nitridation titanium bioactive coating；It specifically includes:
(1) matrix and target: condition are cleaned are as follows: vacuum degree is 1.0~5.0 × 10-5Pa, control glow discharge air pressure are
0.6~1.5Pa, substrate bias are -800.0~-1000.0V, utilize 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) deposit titanium prime coat: condition are as follows: control sputtering pressure is 0.5~1.5Pa, substrate bias for -200.0~-
800.0V, argon flow be 50.0~200.0sccm, DC current be 1.0~5.0A, sputtering sedimentation 2.0~5.0 minutes；
(3) depositing TiN gradient transition and TiN layer: condition are as follows: continue the deposition process of above-mentioned steps (2), to be 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 final nitrogen flow is maintained to deposit 10.0~20.0 minutes；
(4) alloy/hydroxylapatite gradient transition zone: condition is deposited are as follows: control sputtering pressure is 0.5~1.5Pa, with every 5.0 points
Clock interval increase by 100.0~300.0W of radio-frequency power, reduce by 0.5~1.0A of DC current, 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 are -50.0~-200.0V；
(5) deposited porous hydroxyapatite layer: condition are as follows: use hydroxyapatite target, rf sputtering power be 200~
600W, sputtering pressure be 0.5~2.0Pa, argon flow be 100.0~300.0sccm, substrate bias be -50.0~-
300.0V, sedimentation time are 2.0~6.0 hours.
Step 4 post-processes obtained coating: carrying out under atmospheric environment, with the speed of 1.0~5.0 DEG C/min
It is heated to 400.0~800.0 DEG C and keeps the temperature 3.0~6.0 hours；Finally maskable harmful ion release is obtained in matrix surface
Porous hydroxyapatite/nitridation titanium bioactive coating.
Below with reference to specific implementation case, the present invention is further illustrated, but experimental method and ginseng in case study on implementation
Number is without limiting implementation of the invention.
Embodiment 1:
Using frequently as bone plate, bone nail, prosthetic replacement's material Ti-6Al-4V alloy as basis material and according to
Following steps carry 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 is polished, and is soaked in after then respectively cleaning 30.0min with distilled water, alcohol and acetone respectively
24.0 hours in the KOH lye of 3.0mol/L, then proceed to distilled water ultrasonic cleaning 40.0 minutes, finally at 40.0 DEG C
Under environment dry 24.0 hours it is spare.
(2) matrix and target are cleaned, 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, flow 100.0sccm are passed through into sputtering chamber, and maintenance sputtering chamber ar pressure is
0.6Pa, adjustment matrix location make it back to target；Opening grid bias power supply load bias is -800V, is carried out 20.0 minutes to matrix
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 are 2.0A, and hydroxyapatite target power output is 200.0W, and scavenging period is 30.0 minutes.
(3) titanium prime coat is deposited, adjustment matrix makes its face 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 that 0.6Pa, flow 100.0sccm sink to matrix deposition Ti prime coat
The product time is 3.0 minutes.
(4) depositing TiN gradient transition and TiN layer, maintaining previous step to sputter indoor total pressure is 0.6Pa, total gas
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 are 3.0A, and bias is -500.0V, and maintaining nitrogen flow is that 14.0sccm is deposited 15.0 minutes.
(5) alloy/hydroxylapatite gradient transition zone is deposited, control sputtering pressure is 0.6Pa, increases with every 5.0 minutes intervals and penetrates
Frequency power 100.0W reduces DC current 1.0A, nitrogen flow 5.0sccm and substrate bias -150.0V, until DC current and
Nitrogen flow is 0, radio-frequency power 300.0W, and substrate bias is -50.0V.
(6) hydroxyapatite layer is deposited, nitrogen and titanium target power supply are closed, it is 0.8Pa that adjustment, which sputters indoor ar pressure,
Control argon flow is 150.0sccm, and hydroxyapatite target sputtering power is 300.0W, and bias is -50.0V, and sedimentation time is
3.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating post-processes, and under atmospheric environment, is heated to 600.0 DEG C with the heating rate of 3.0 DEG C/min and keeps the temperature
3.0 hours, then cool to room temperature with the furnace.Finally maskable harmful ion release is obtained on Ti-6Al-4V alloy substrate surface
Porous hydroxyapatite/nitridation titanium bioactive coating.
Embodiment 2:
Using frequently as bone plate, bone nail, prosthetic replacement's material 316L stainless steel as basis material and according to such as
Lower step carries out:
(1) by 316L stainless steel cut at 30.0 × 30.0 × 2.0mm3Disk, with 400#, 800#, 1200# diamond
Sand paper is polished and is polished, and is then cleaned 30.0 minutes with distilled water, alcohol and acetone, is finally done in the environment of 40.0 DEG C respectively
Dry 24.0 hours spare.
(2) matrix and target are cleaned, 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, flow 120.0sccm are passed through into sputtering chamber, and maintenance sputtering chamber ar pressure is
0.8Pa, adjustment matrix location make it back to target；Opening grid bias power supply load bias is -1000.0V, carries out 30.0 to matrix
Minute argon ion Discharge Cleaning and activation；Grid bias power supply is closed, opens titanium target and hydroxyapatite target power supply 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 prime coat is deposited, adjustment matrix makes its face 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 that 0.8Pa, flow 120.0sccm sink to matrix deposition titanium prime coat
The product time is 3.0 minutes.
(4) depositing TiN gradient transition and TiN layer, adjusting and sputtering indoor total pressure is 0.8Pa, 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 are 3.0A, and bias is -500.0V, and maintaining nitrogen flow is that 15.0sccm is deposited 15.0 minutes.
(5) alloy/hydroxylapatite gradient transition zone is deposited, control sputtering pressure is 1.0Pa, increases with every 5.0 minutes intervals and penetrates
Frequency power 150.0W reduces DC current 1.0A, nitrogen flow 5.0sccm and substrate bias -140.0V, until DC current and
Nitrogen flow is 0, radio-frequency power 450.0W, and substrate bias is -80.0V.
(6) hydroxyapatite layer is deposited, nitrogen and titanium target power supply are closed, it is 1.2Pa that adjustment, which sputters indoor ar pressure,
Control argon flow is 120.0sccm, and hydroxyapatite target sputtering power is 450.0W, and bias is -80.0V, and sedimentation time is
4.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating post-processes, and under atmospheric environment, is heated to 600.0 DEG C with the heating rate of 3.0 DEG C/min and keeps the temperature
5.0 hours, then cool to room temperature with the furnace.Finally the more of maskable harmful ion release are obtained on 316L stainless steel base surface
Hole hydroxyapatite/nitridation titanium bioactive coating.
Embodiment 3:
It as basis material and is followed the steps below using the CoCrMo alloy frequently as prosthetic replacement's material:
(1) CoCrMo alloy substrate is cut into 30.0 × 3.0mm of φ3Disk, with 400#, 800#, 1200#, 1500#
Diamond sand paper is polished and is polished, and is soaked in after then cleaning 30.0 minutes with distilled water, alcohol and acetone respectively
24.0 hours in the KOH lye of 3.0mol/L, then proceed to distilled water ultrasonic cleaning 40.0 minutes, finally at 40.0 DEG C
Under environment dry 24.0 hours it is spare.
(2) by process cleaning target and matrix described in step 2 in embodiment 2.
(3) titanium prime coat is deposited, adjustment matrix makes its face 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 that 0.8Pa, flow 150.0sccm sink to matrix deposition titanium prime coat
The product time is 2.0 minutes.
(4) depositing TiN gradient transition and TiN layer, it is 0.6Pa that adjustment, which sputters indoor total pressure, 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 are 3.0A, and bias is -500.0V, and maintaining nitrogen flow is that 20.0sccm is deposited 10.0 minutes.
(5) alloy/hydroxylapatite gradient transition zone is deposited, control sputtering pressure is 1.2Pa, increases with every 5.0 minutes intervals and penetrates
Frequency power 80.0W reduces DC current 0.8A, nitrogen flow 5.0sccm and substrate bias -100.0V, until DC current and
Nitrogen flow is 0, radio-frequency power 320.0W, and substrate bias is -100.0V.
(6) hydroxyapatite layer is deposited, nitrogen and titanium target power supply are closed, it is 2.0Pa that adjustment, which sputters indoor ar pressure,
Control argon flow is 150.0sccm, and hydroxyapatite target sputtering power is 320.0W, and bias is -100.0V, and sedimentation time is
3.0 hours, natural cooling 3.0 hours after the completion of deposition.
(7) coating post-processes, and under atmospheric environment, is heated to 600.0 DEG C with the heating rate of 4.0 DEG C/min and keeps the temperature
4.0 hours, then cool to room temperature with the furnace.Finally the more of maskable harmful ion release are obtained on CoCrMo alloy substrate surface
Hole hydroxyapatite/nitridation titanium bioactive coating.
Fig. 3 is X of the gained porous hydroxyapatite/nitridation titanium bioactive coating after heat treatment in embodiment 1
X ray diffraction map is clearly present the characteristic diffraction peak of hydroxyapatite in figure, after coating is by heat treatment, the crystallinity of coating
It can greatly improve, can effectively reduce the solution rate of coating, stability and bioactivity will enhance.
Fig. 4 is Ti-6Al-4V matrix surface deposited porous hydroxyapatite/nitridation titanium bioactive coating front and back 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 substrate corrodes, and reduce the corrosion rate of matrix, thus can reduce
The release of the harmful ions such as corrosion product Al, V.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of porous hydroxyapatite/nitridation titanium bioactive coating of maskable harmful ion release, it is characterised in that: institute
State coating include the titanium prime coat being arranged from inside to outside, it is TiN gradient transition, TiN layer, alloy/hydroxylapatite gradient transition zone, porous
Hydroxyapatite layer, the porous hydroxyapatite layer have mesoporous nano structure；
The coating is prepared by the following steps to obtain:
Step 1, first preparation titanium target, and prepare hydroxyapatite target；Using high purity titanium as titanium target；Hydroxyapatite target
Material is used having a size of (10.0~30.0) × 40.0 × 10.0mm3Fritter be spliced, hydroxyapatite fritter is by partial size
0.1 ~ 5.0 μm of hydroxyapatite powder uses load for 50.0 ~ 100.0KN under argon atmosphere, temperature 1000.0
It is pressed within pressure maintaining 3.0~5.0 hours at ~ 1500.0 DEG C；
Step 2 pre-processes matrix；
Pretreated matrix is placed in deposited porous in more target position magnetron sputtering vapor depositing system vacuum sputterings room by step 3
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 post-processes obtained coating.
2. porous hydroxyapatite/titanium nitride biological active coating of maskable harmful ion release according to claim 1
Layer, it is characterised in that: the titanium prime coat with a thickness of 20.0 ~ 100.0nm；TiN gradient transitional lay is with a thickness of 0.5 ~ 2.0 μm；
TiN layer with a thickness of 0.5 ~ 3.0 μm；Alloy/hydroxylapatite gradient transition zone with a thickness of 0.5~2.0 μm；Porous hydroxyapatite
Layer is with a thickness of 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: the diameter of the mesoporous nano of the porous hydroxyapatite layer is 15.0 ~ 60.0nm.
4. a kind of porous hydroxyapatite/nitridation titanium bioactive coating preparation method of maskable harmful ion release,
It is characterized in that: the following steps are included:
Step 1, first preparation titanium target, and prepare hydroxyapatite target；Using high purity titanium as titanium target；Hydroxyapatite target
Material is used having a size of (10.0~30.0) × 40.0 × 10.0mm3Fritter be spliced, hydroxyapatite fritter is by partial size
0.1 ~ 5.0 μm of hydroxyapatite powder uses load for 50.0 ~ 100.0KN under argon atmosphere, temperature 1000.0
It is pressed within pressure maintaining 3.0~5.0 hours at ~ 1500.0 DEG C；
Step 2 pre-processes matrix；
Pretreated matrix is placed in deposited porous in more target position magnetron sputtering vapor depositing system vacuum sputterings room by step 3
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 post-processes 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 2, the step of substrate pretreated are as follows:
Matrix blank is cut into required shape by the first step, is then used diamond sand paper to carry out sanding and polishing, made
Its surface roughness is less than 50.0nm, then uses distilled water respectively, alcohol and acetone respectively clean 30.0 minutes；
Cleaned matrix is placed in the KOH lye that concentration is 2.0 ~ 5.0mol/L and impregnates 24.0 hours, at lye by second step
Continue after reason with distilled water ultrasonic cleaning 40.0 minutes, finally in the environment of 40.0 DEG C dry 24.0 hours it is spare.
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: the specific steps of step 3 are as follows:
The first step cleans matrix and target: condition are as follows: vacuum degree is 1.0 ~ 5.0 × 10-5Pa, control glow discharge air pressure are 0.6
~ 1.5Pa, substrate bias are -800.0 ~ -1000.0V, utilize argon plasma sputter clean activated matrix；Grid bias power supply is closed,
It opens titanium target and hydroxyapatite target power supply and Glow Discharge Cleaning is carried out to target material surface；
Second step deposits titanium prime coat: condition are as follows: control sputtering pressure is 0.5 ~ 1.5Pa, substrate bias for -200.0 ~ -
800.0V, argon flow be 50.0 ~ 200.0sccm, DC current be 1.0 ~ 5.0A, sputtering sedimentation 2.0 ~ 5.0 minutes；
Third step, depositing TiN gradient transition and TiN layer: condition are as follows: continue above-mentioned second step deposition process, between being per minute
It is passed through nitrogen into vacuum sputtering room every the speed for increasing by 1.0 ~ 5.0sccm, until nitrogen flow is 10.0 ~ 20.0sccm, and
Final nitrogen flow is maintained to deposit 10.0 ~ 20.0 minutes；
4th step deposits alloy/hydroxylapatite gradient transition zone: condition are as follows: control sputtering pressure is 0.5 ~ 1.5Pa, with every 5.0 points
Clock interval increases by 100.0 ~ 300.0W of radio-frequency power, reduces by 0.5 ~ 1.0A of DC current, 3.0 ~ 5.0sccm of nitrogen flow and matrix
Bias -100.0 ~ -200.0V, until DC current and nitrogen flow are 0sccm, radio-frequency power is 200.0 ~ 600.0W, matrix
Bias is -50.0 ~ -200.0V；
5th step, deposited porous hydroxyapatite layer: condition are as follows: use hydroxyapatite target, rf sputtering power be 200 ~
600W, sputtering pressure are 0.5 ~ 2.0Pa, and argon flow is 100.0 ~ 300.0sccm, and substrate bias is -50.0 ~ -300.0V, are sunk
The product time is 2.0 ~ 6.0 hours.
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: in step 4, the post-processing step of coating are as follows: it is carried out under atmospheric environment, with 1.0 ~
The speed of 5.0 DEG C/min is heated to 400.0 ~ 800.0 DEG C and keeps the temperature 3.0 ~ 6.0 hours.
8. any porous hydroxyapatite/nitridation titanium bioactive coating of claim 1-3 is used for bio-medical metal
Purposes in terms of the release of material shields harmful ion and improvement bioactivity.
9. purposes according to claim 8, it is characterised in that: the biomedical metallic material include medical stainless steel,
CoCrMo alloy, NiTi alloy, magnesium alloy and pure titanium or titanium alloy.
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| 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 |
| CN110512249B (en) * | 2018-05-22 | 2021-04-27 | 南京理工大学 | Preparation method of titanium carbonitride and hydroxyapatite composite coating |
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