CN106902390A - A kind of titanium alloy is implanted into composite material and its preparation and application - Google Patents
A kind of titanium alloy is implanted into composite material and its preparation and application Download PDFInfo
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- CN106902390A CN106902390A CN201611257903.3A CN201611257903A CN106902390A CN 106902390 A CN106902390 A CN 106902390A CN 201611257903 A CN201611257903 A CN 201611257903A CN 106902390 A CN106902390 A CN 106902390A
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- Prior art keywords
- titanium alloy
- arc oxidation
- implant
- layer
- composite material
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- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 106
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 106
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 88
- 239000007943 implant Substances 0.000 claims abstract description 84
- 230000003647 oxidation Effects 0.000 claims abstract description 81
- 238000004070 electrodeposition Methods 0.000 claims abstract description 41
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
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- 239000004626 polylactic acid Substances 0.000 claims abstract description 35
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 34
- 239000011737 fluorine Substances 0.000 claims abstract description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000002513 implantation Methods 0.000 claims abstract description 27
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- 238000005470 impregnation Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 43
- 239000008367 deionised water Substances 0.000 claims description 37
- 229910021641 deionized water Inorganic materials 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 24
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 23
- 239000000843 powder Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052719 titanium Inorganic materials 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
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- 235000019441 ethanol Nutrition 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
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- 229940075397 calomel Drugs 0.000 claims 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims 1
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Classifications
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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- A—HUMAN NECESSITIES
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/50—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
- A61L27/56—Porous materials, e.g. foams or sponges
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- G06T11/008—Specific post-processing after tomographic reconstruction, e.g. voxelisation, metal artifact correction
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- 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
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/412—Tissue-regenerating or healing or proliferative agents
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- 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
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Abstract
The invention discloses a kind of titanium alloy implantation composite material and its preparation and application, the titanium alloy implantation composite material is titanium alloy abutment of implant through the model that 3D printing makes with Titanium Powder, differential arc oxidation film layer is formed using micro-arc oxidation on titanium alloy abutment of implant surface, then hydroxyapatite layer or fluorine hydroxyapatite layer are formed using electrochemical deposition method in micro-arc oxidation films layer surface again, finally forms polylactic acid layers in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation；The present invention is from the data acquisition of original impaired bone structure to the preparation of final multicoat composite construction, realize the personalized exploitation of implant material, obtain high-quality titanium alloy implantation composite material, wherein polarization test shows that its corrosion resistance obtains 2~3 liftings of the order of magnitude, and there is the titanium alloy composite material after prepared by osteoblasts cultivation display more preferable osteocyte to promote ability.
Description
(1) technical field
The present invention relates to a kind of titanium alloy multi-layer biological composite with good biocompatibility and preparation method thereof,
I.e. by carrying out the scanning of multi-layer spiral CT to the impaired bone structure of human body, initial data is then carried out into treatment reparation, then pass through
3D printing, differential arc oxidation, electrochemical deposition, boiomacromolecule layer prepare etc. method prepare have titanium alloy/differential arc oxidation film layer/
The implantation composite material of hydroxyapatite (or fluorine hydroxyapatite)/boiomacromolecule Rotating fields.
(2) background technology
Titanium or titanium alloy material is widely used in its good bioactivity, biomechanical property and chemical property
Joint prosthesis and tooth implant field.At present, the method for preparing biological medical titanium alloy mainly includes：Vapour deposition process, powder
Metallurgy method, discharge plasma sintering method etc..But vapour deposition process technological operation degree-of-difficulty factor in preparation process is big, deposition velocity
It is slow and production cost is high, so as to limit its extensive utilization in medical field；Powder metallurgic method is burnt in preparation process
The knot time is short, it is difficult to controls setting rate and is difficult to obtain complex-shaped structure；The preparation of discharge plasma sintering method
Journey is relatively costly and must carry out under vacuum conditions.
And new laser gain material manufacturing technology (3D printing), the not only advantage with high precision and the energy in forming process
Real metallurgical binding is reached, the shortcoming caused by titanium alloy conventional fabrication processes is overcome.3D printing technique is with digital mould
Based on type, with powdery metal or plastic or other material, come the technology of constructed object by way of successively melting and piling up.
Existing bioengineering field can carry out structure of the 3D printing in terms of bone structure by multi-layer spiral CT three-dimensional rebuilding, be based on
The three-dimensional reconstruction of multi-layer spiral CT can sweep the common resolution ratio for improving modality conversion between entity world and digital world
Retouch, edit and replication entity object, create accurate copy or optimization original paper.
Find that titanium or titanium alloy can cause in nearest research and be implanted the scorching without the generation of blood vessel fibr tissue of body cladding
Disease is reacted, while it is poor to there is also conductive, heat conductivility, contacts perishable with other metals, elastic modelling quantity greatly, Metal ion release
The problems such as.In order to solve these problems, hydroxyapatite (HA:Ca10(PO4)6(OH)2) because its have good synosteosis performance,
Biocompatibility and widely paid close attention to.Hydroxyapatite has similar chemical composition and crystal structure with bone tissue, this
Just there is larger adhesive force in a short time after planting material implantation organism, material/bone interface can be made to form strong bonded, have
Beneficial to the initial maintenance of graft materials, can effectively suppress metal ion to the release in organism, hydroxyapatite may be used also in addition
To extend the service life of implant.But hydroxyapatite is easy to fatigue failure, for load implant, hydroxyapatite coat
Layer is even more and is easily come off from implant.Research shows that hydroxyapatite poor mechanical properties, its bending strength in itself is less than
100MPa.This can substantially reduce the success rate that implant is implanted into vivo.
Differential arc oxidization technique (Micro-arc oxidation, MAO) is the modified skill in surface that a kind of newly-developed gets up
Art, the technology is that parent metal is directly become oxide ceramics by micro-arc discharge area instantaneous high-temperature high-pressure sinter, and is obtained
Thicker oxidation film.The activation of titanium surface oxide film is most promising one kind in current tooth-planting material surface activation
Method, can significantly improve the binding ability of stability of the titanium alloy in human body, lifting hydroxyapatite layer and matrix.At present
Titanium surface oxide film activation it is important that how to form the oxidation film of surface hydroxyl apatite, usual way has two
Kind：One is titanium surface active coating, i.e., processed by differential arc oxidation and directly generated with bioactivity in titanium alloy surface
Hydroxyapatite coating layer；Another is that titanium surface active is modified, i.e., after processing metal surface, anatase is formed on titanium surface
Or rutile TiO2Film, then by material be placed in physiological environment or simulation physiological environment in its spatial induction HA formation.So
And both approaches are for preparing environment with requirement higher.The activation modification on titanium surface needs the ring at 120 DEG C among these
Carried out under border and there is requirement higher to operating environment, which has limited further applying for hydroxyapatite coating layer.
The preparation of hydroxyapatite is carried out to the titanium alloy substrate of differential arc oxidation pre-treatment using electrochemical deposition, more at present
Common hydro-thermal method prepares hydroxyapatite and compares with hot spray process, and the method can significantly reduce preparation temperature, improves experiment
Operability, is conducive to the popularization of titanium alloy/hydroxyapatite composite material.But the meeting in performance of simple electrodeposited coating
There is caducous tendency, causing the service life of coating reduces.Therefore, it is further to improve electro-deposition hydroxyapatite coating layer
Adhesion and composite biocompatibility, the hydroxyapatite layer to surface can carry out the system of boiomacromolecule coating
It is standby.The present invention carries out multi-slice Spiral CT three-dimensional reconstruction by original bone structure, and titanium conjunction is carried out using 3D printing technique
The preparation of golden material, the differential arc oxidation for then carrying out surface to it is processed to improve the corrosion resistance of titanium alloy substrate, and to connect
The coating for getting off is prepared and prepared.Prepared by the electrochemical deposition that hydroxyapatite coating layer is carried out in electrochemical deposition liquid, go forward side by side
The film preparation of row boiomacromolecule layer, the system of titanium alloy multi-layer biological composite is realized by a series of PROCESS FOR TREATMENT
It is standby, obtain matching high, high performance composite construction.And so far, this systemic, high reproducibility, the titanium of high-compatibility
The preparation of alloy laminated coating implant has not been reported.
(3) content of the invention
It is an object of the present invention to provide a kind of titanium alloy multi-layer biological composite with good biocompatibility and its system
Preparation Method and application, based on multi-layer spiral CT three-dimensional rebuilding, carry out the 3D printing of titanium alloy implant and to preparing
Titanium alloy implant carries out a series of surface treatments such as differential arc oxidation, electro-deposition and boiomacromolecule layer preparation and prepares titanium conjunction
The composite of gold/differential arc oxidation film layer/hydroxyapatite (HAP) or fluorine hydroxyapatite (FHAP)/boiomacromolecule layer.
The technical solution adopted by the present invention is：
The present invention provides a kind of titanium alloy implantation composite material, and the titanium alloy is implanted into composite material with Titanium Powder
The model made through 3D printing is titanium alloy abutment of implant, is formed using micro-arc oxidation on titanium alloy abutment of implant surface
Differential arc oxidation film layer (i.e. bio-ceramic coating), then forms hydroxyl in micro-arc oxidation films layer surface using electrochemical deposition method again
Apatite layer or fluorine hydroxyapatite layer, finally form PLA in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation
Layer (i.e. boiomacromolecule layer)；Differential arc oxidation liquid composition is used by the micro-arc oxidation：8~12g/L Na2SiO3, 8~12g/
L Na3PO4, 6~10g/L NaOH, 3~7g/L KF, 3~8g/L Na2CO3, the anhydrous second of 1~5g/L KOH, 50~100mL/L
Alcohol, solvent is deionized water, pH value nature；Electrochemical deposition liquid composition is used by the hydroxyapatite layer：0.042mol/L
Ca(NO3)2、0.5mol/L NaNO3、0.025mol/L NH4H2PO4, 30-50mL/L absolute ethyl alcohols, 30-50mL/L hydrogen peroxide,
0.004-0.006mol/L APES OP-21,0.1-0.2mol/L trisodium citrates, solvent is deionized water,
It is 3-5 with trometamol and nitre acid for adjusting pH；The fluorine hydroxyapatite layer electrochemical deposition liquid is to hydroxyapatite layer institute
With addition 0.0008mol/L NaF in electrochemical deposition liquid.
Further, preferably differential arc oxidation liquid composition is：10g/L Na2SiO3、10g/L Na3PO4、8g/L NaOH、5g/L
KF、6g/L Na2CO3, 3g/L KOH, 75mL/L absolute ethyl alcohols, solvent is deionized water, pH value nature；The electrochemical deposition
Liquid is constituted：0.042mol/L Ca(NO3)2、0.025mol/L NH4H2PO4、0.5mol/L NaNO3, 40mL/L absolute ethyl alcohols,
Hydrogen peroxide 40mL/L, 0.005mol/L APES OP-21,0.1mol/L trisodium citrate, solvent is deionization
Water, is 4 with trometamol and nitre acid for adjusting pH.
Further, preferably described differential arc oxidation film layer thickness is 20 μm~30 μm, the hydroxyapatite layer or fluorine hydroxyl
Apatite layer thickness is 3 μm~5 μm.
Further, preferably described differential arc oxidation film layer is prepared as follows：It is with described titanium alloy abutment of implant
Anode, stainless steel is negative electrode, is 550~650Hz in frequency in differential arc oxidation liquid, and the differential of the arc time is 15~30min, duty
Than being 15~30%, current density is 15-25A/cm2, operation temperature is that (optimized frequency is 600Hz, differential of the arc time to room temperature
20min, dutycycle is 20%, and current density is 20A/cm2, operation temperature be 23 DEG C) under the conditions of carry out differential arc oxidation reaction, instead
Titanium alloy substrate is taken out after should terminating, is cleaned by ultrasonic in deionized water, dried in the 20-45 DEG C of baking oven of (preferably 45 DEG C),
The titanium alloy abutment of implant that surface forms differential arc oxidation film layer is obtained, titanium alloy abutment of implant/differential arc oxidation film layer is designated as.
Further, preferably described hydroxyapatite layer or fluorine hydroxyapatite layer are prepared as follows：Formed with surface
The titanium alloy abutment of implant of differential arc oxidation film layer is working electrode, and, used as to electrode, saturated calomel electrode is used as reference for platinized platinum
Electrode, in electrochemical deposition liquid, constant current mode, current density is 0.39~0.59mA/cm2(preferably 0.49mA/cm2), deposition
Temperature is to carry out electrochemical deposition 60-120min (preferably 60 DEG C deposition 90min) under conditions of 50-70 DEG C after, by described titanium
Alloy abutment of implant is taken out, and is washed with deionized water only, and room temperature is dried；The NaOH water of 1-2mol/L (preferably 2mol/L) is immersed again
In solution, 2-4h is soaked at 80 DEG C, then cleaned repeatedly with deionized water, after room temperature is dried, in argon gas or vacuum protection
The high temperature anneal is carried out under atmosphere in tube furnace, 500 DEG C are warming up to the speed of 10 DEG C/min, be incubated 2h, obtain surface
The titanium alloy implant base of differential arc oxidation film layer, hydroxyapatite layer or fluorine hydroxyapatite Rotating fields is sequentially formed from the inside to the outside
Body, is designated as titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer.If preparing fluorine hydroxyl
Base apatite layer, adds 0.0008mol/L NaF in electrochemical deposition liquid.
Further, the thickness of preferably described polylactic acid layers is 5 μm~10 μm.
Further, preferably described polylactic acid layers are prepared as follows：Polylactic acid powder is added in dichloromethane, room
The lower uniform stirring of temperature 6 hours, obtains the PLA solution of mass fraction 2.5%；The polylactic acid powder and dichloromethane solvent
Mass ratio is 2.5：97.5；Surface is sequentially formed hydroxyapatite layer or fluorine hydroxyapatite layer, differential arc oxidation from outside to inside
In the titanium alloy abutment of implant immersion PLA solution of film layer, after soaking at room temperature 20-30s (preferably 25s), with 15-25mm/
The constant speed of min (preferably 20mm/min) proposes that room temperature is dried in ventilating kitchen, and then deionized water is cleaned, and room temperature is dried,
Obtain and sequentially form polylactic acid layers, hydroxyapatite layer or fluorine hydroxyapatite layer, the titanium of differential arc oxidation film layer from outside to inside
Alloy is implanted into composite material.
Further, preferably described titanium alloy abutment of implant is prepared as follows：(1) impaired bone structure is carried out into CT to sweep
Retouch, obtain the CT scan data of impaired bone structure, and be input to Materialise 3 d modeling softwares, carry out threshold value division, so
The noise for importing image is removed using region growth method afterwards, removal, the segmentation both injured bones structural region of redundant data is carried out；(2)
Segmentation is felt better behind damage bone structure region, further obtains impaired bone structure by Materialise 3 d modeling softwares opening operation
Three-dimensional structure data, realization initial data is switched into three-dimensional structure data, then will obtain three-dimensional structure data input UG
Software, obtains digitlization Cranial defect threedimensional model；(3) according to digitlization Cranial defect threedimensional model, design bone using CAD software and lack
Module is damaged, STL models are obtained；(4) titanium alloy powder is well mixed in ball mill, mill rotating speed is 250r/min, during ball milling
Between be 30min, and it is protective gas to employ nitrogen as, and obtains the titanium alloy powder after ball milling, and particle diameter is 70 μm~80 μm；Will
STL mode input 3D printers, and the titanium alloy powder after ball milling is added into 3D printer, it is molded using laser 3D printing, swash
The power of light be 200~300W, 1200~1500mm/s of sweep speed, 1~3ms of pulsewidth, frequency 0.0Hz, 2~3mm of defocusing amount,
(preferably the power of laser is 200W, sweep speed 1200mm/s, pulsewidth 2ms, frequency 0.0Hz, defocusing amount to spot diameter 0.5mm
2.5mm, spot diameter 0.5mm), printed under argon gas or vacuum protection atmosphere, individual layer print thickness 0.04mm, the embryo material of acquisition
Electrochemical polish is carried out after being incubated 6-8h at 550-800 DEG C, polishing fluid is volume ratio 1:3:6 perchloric acid, n-butanol and methyl alcohol
Mixed liquor, using electrochemical workstation (IviumStat) and be provided with agitating device electrolytic cell in constant current mode, current density
10~20A/dm2(preferably 15A/dm2), -30 degrees Celsius of temperature (plus liquid nitrogen cooling), 100~200r/min of mixing speed is (preferably
Operation is polished under conditions of 150r/min), then uses absolute alcohol, acetone and deionized water to be cleaned by ultrasonic successively, room temperature is done
It is dry, obtain described titanium alloy abutment of implant.
Further, preferably described Titanium Powder be Ti-6Al-4V titanium alloy powders, particle diameter be 100 μm~120 μm, Ti-
6Al-4V Titanium Powders mass percent is constituted：Fe≤0.30%, C≤0.10%, N≤0.05%, H≤0.015%, O≤
0.20%, Al：5.5%~6.8%, V：3.5%~4.5%, remaining is Ti.
The present invention also provides the preparation method that a kind of titanium alloy is implanted into composite material, and methods described is：(1) will receive
Damaging bone structure carries out CT scan, obtains the CT scan data of impaired bone structure, and it is soft to be input to Materialise three-dimensional modelings
Part, carries out threshold value division, and the noise for importing image is then removed using region growth method, carries out removal, the segmentation of redundant data
Both injured bones structural region；(2) after damage bone structure region is felt better in segmentation, further opened by Materialise 3 d modeling softwares
Computing obtains the three-dimensional structure data of impaired bone structure, and initial data is switched to three-dimensional structure data by realization, then by acquisition
Three-dimensional structure data is input into UG softwares, obtains digitlization Cranial defect threedimensional model；(3) according to digitlization Cranial defect threedimensional model,
Cranial defect module is designed using CAD software, STL models are obtained；(4) by titanium alloy powder, in ball mill, (XQM-0.4L is planetary
Ball mill) in be well mixed, mill rotating speed be 250r/min, Ball-milling Time is 30min, and it is protective gas to employ nitrogen as,
The titanium alloy powder after ball milling is obtained, particle diameter is 70 μm~80 μm；By STL mode input 3D printing equipment, and by after ball milling
Titanium alloy powder is placed in 3D printing equipment, is molded using laser 3D printing, and the power of laser is 200~300W, sweep speed
1200~1500mm/s, 1~3ms of pulsewidth, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.5mm (the preferred power of laser
Be 200W, sweep speed 1200mm/s, pulsewidth 2ms, frequency 0.0Hz, defocusing amount 2.5mm, spot diameter 0.5mm), argon gas or
Printed under vacuum protection atmosphere, individual layer print thickness 0.04mm, the embryo material of acquisition carries out electrification after being incubated 6-8h at 550-800 DEG C
Optical polishing, polishing fluid is volume ratio 1:3:6 perchloric acid, n-butanol and methyl alcohol mixed liquor, using electrochemical workstation and are furnished with
The electrolytic cell of agitating device is in constant current mode, 10~20A/dm of current density2, -10 DEG C, 100~200r/min's of mixing speed
Under the conditions of be polished operation, then be cleaned by ultrasonic with absolute alcohol, acetone and deionized water successively, dry at room temperature, obtain institute
The titanium alloy abutment of implant stated；(5) with described titanium alloy abutment of implant as anode, stainless steel is negative electrode, in differential of the arc oxygen
Change in liquid, frequency is 550~650Hz, the differential of the arc time is 15~30min, and dutycycle is 15~30%, and current density is 15-
25A/cm2, to carry out differential arc oxidation reaction under room temperature condition, described titanium alloy implant is taken out in reaction to operation temperature after terminating
Matrix, is cleaned by ultrasonic in deionized water, is dried in 20-45 DEG C of baking oven, obtains the titanium that surface forms differential arc oxidation film layer
Alloy implant, is designated as titanium alloy abutment of implant/differential arc oxidation film layer；(6) with step (5) titanium alloy abutment of implant/micro-
Arc oxidation film layer is working electrode, platinized platinum as to electrode, saturated calomel electrode as reference electrode, in electrochemical deposition liquid
In, constant current mode, current density is 4-6mA/cm2, depositing temperature be 37 DEG C under conditions of carry out electrochemical deposition 90-150min
Afterwards, described titanium alloy abutment of implant/differential arc oxidation film layer is taken out, is washed with deionized water only, room temperature is dried；1- is immersed again
In the NaOH aqueous solution of 2mol/L, 2-4h is soaked at 80 DEG C, then cleaned repeatedly with deionized water, after room temperature is dried, in argon
The high temperature anneal is carried out under gas or vacuum protection atmosphere in tube furnace, 200 DEG C are warming up to the speed of 10 DEG C/min, protected
Warm 2h, obtains surface and sequentially forms differential arc oxidation film layer, hydroxyapatite layer or fluorine hydroxyapatite Rotating fields from the inside to the outside
Titanium alloy abutment of implant, is designated as titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite
Layer；(7) polylactic acid powder is added in dichloromethane, room temperature uniform stirring 6 hours, obtains the poly- breast of mass fraction 2.5%
Acid solution；Step (6) titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer are soaked
Enter in PLA solution, after soaking at room temperature 20-30s, propose that room temperature is dried in the air in ventilating kitchen with the constant speed of 15-25mm/min
Dry, then deionized water is cleaned, and room temperature is dried, that is, obtain and sequentially form from outside to inside polylactic acid layers, hydroxyapatite layer or fluorine
The titanium alloy implantation composite material of hydroxyapatite layer, differential arc oxidation film layer.
Additionally, the present invention also provides a kind of titanium alloy implantation composite material answering in bone renovating material is prepared
With.
Room temperature of the present invention refers to 25-30 DEG C.Differential arc oxidation film layer, hydroxyapatite layer or fluorine hydroxyl phosphorus in the present invention
Grey rock layers control thickness, the thickness of polylactic acid layers to be controlled by impregnating repeatedly, lifting by the reaction time.
Compared with the existing technology for preparing titanium alloy implant, the beneficial effects are mainly as follows：
(1) present invention is solved using the 3D printing technique based on multi-layer spiral CT three-dimensional rebuilding in the preparation of matrix
Complex process caused by the preparation methods such as conventional cast, sintering, titanium alloy is oxidizable, the low problem of implant recovery accuracy,
Improve the structure precision and biocompatibility of titanium alloy implant；
(2) present invention prepares bio-ceramic coating and can in the coating introduce calcium using differential arc oxidization technique in titanium alloy surface
Deng the element favourable to bone growth, obtaining special micrometer level porous controllable hole can strengthen the machine of histocyte and implant
Tool binding ability, and excellent binding ability can meet the wearability demand of titanium alloy implant clinical manipulation and the length of film layer
Effect property；
(2) method that the titanium alloy surface using electro-deposition techniques after differential arc oxidation treatment prepares hydroxyapatite coating layer
The methods such as more traditional plasma spraying have low-temperature operation, and process is simple can be in the substrate of complex-shaped and porous surface
The advantage of uniform coating is prepared, while the introducing of hydroxyapatite coating layer enhances the hydrophily of film surface, is conducive to albumen
In the absorption on surface, significantly improve the migration of cell and increase, improve the Integrated implant of material, so as to be conducive to healing for bone tissue
Close；
(3) present invention carries out surface macromolecule layer using Best-Effort request machine to the titanium alloy implant after electrodeposition process
Prepare, improve coating corrosion resistance in vivo, further promote the reparation of bone tissue.
Data acquisition from original impaired bone structure of the invention realizes implantation to the preparation of final multicoat composite construction
The personalized exploitation of body material, obtains high-quality titanium alloy implantation composite material, wherein polarization test shows its anti-corruption
Corrosion can obtain 2~3 liftings of the order of magnitude, and the titanium alloy composite material after prepared by osteoblasts cultivation display has preferably
Osteocyte promotes ability.
(4) illustrate
Fig. 1 is that titanium alloy/differential arc oxidation film layer/hydroxyapatite (or fluorine hydroxyapatite)/polylactic acid layers of the present invention are planted
Enter the structural representation of composite material；
Fig. 2 is that titanium alloy abutment of implant carries out surface magnification after differential arc oxidation and be 1000 times sweeping in embodiment 1
Retouch electromicroscopic photograph；
Fig. 3 is the scanning electricity that titanium alloy abutment of implant carries out surface after differential arc oxidation and electrochemical deposition in embodiment 1
After mirror figure, wherein a are to amplify 1000 times, after b is to amplify 5000 times；
Fig. 4 is after titanium alloy abutment of implant carries out differential arc oxidation and electrochemical deposition respectively in embodiment 2, surface with go
The contact angle of ionized water contact, a is the contact angle with deionized water after differential arc oxidation, b be after differential arc oxidation, chemical deposition with go
The contact angle of ionized water；
Fig. 5 is the scanning electricity that titanium alloy abutment of implant carries out surface after differential arc oxidation and electrochemical deposition in embodiment 2
After mirror figure, wherein a are to amplify 1000 times, after b is to amplify 10000 times；
Fig. 6 is that titanium alloy substrate carries out the XRD spectra after differential arc oxidation and electrochemical deposition in embodiment 2.
(5) specific embodiment
With reference to specific embodiment, the present invention is described further, but protection scope of the present invention is not limited in
This：
In following examples, titanium alloy implantation composite material of the invention has the structural representation of laminated coating (as schemed
1), including differential arc oxidation film layer, hydroxyapatite (or fluorine hydroxyapatite) and PLA boiomacromolecule layer.
Embodiment 1
1st, the preparation of titanium alloy abutment of implant
(1) patient's bone structure is carried out into CT scan (slices spiral CTs of GE LightSpeed 16), carries out both injured bones structure number
According to collection, data save as DICOM format；
(2) CT scan data of acquisition is input to Materialise 3 d modeling softwares (Materialise
Magics20), threshold value division is carried out, the noise for importing image is then removed using region growth method, carry out going for redundant data
Except, segmentation both injured bones structural region；
(3) three-dimensional structure data of impaired bone structure is obtained by Materialise 3 d modeling softwares opening operation, then
The three-dimensional data that will be obtained is input into UG softwares (NX9.0) and obtains digitlization Cranial defect threedimensional model, and the reparation for carrying out Cranial defect sets
Meter；
(4) being designed according to Cranial defect and the limbs line of force using CASE(Computer Aided Software Engineering) (CAD) (AutoCAD2010) carries out bone
The design of defect module, obtains high-quality digital model.
(5) the digital model data that will be obtained with the object STL mode inputs of standard to 3D printer, (grind by Central China University of Science and Technology
The type SLM systems of HRPM- II of system) in, by Ti-6Al-4V, (constituent mass percentage is：Fe≤0.30%, C≤0.10%, N≤
0.05%, H≤0.015%, O≤0.20%, Al：5.5%~6.8%, V：3.5%~4.5%, remaining is Ti) Titanium Powder
Last (100 μm~120 μm of particle diameter) is well mixed in ball mill (XQM-0.4L planetary ball mills), and mill rotating speed is
250r/min, Ball-milling Time is 30min, and it is protective gas to employ nitrogen as, and obtains the titanium alloy powder after ball milling, particle diameter
It is 70 μm~80 μm.Titanium alloy powder after ball milling is added into 3D printer, is molded using laser 3D printing, the power of laser is
200W, sweep speed 1200mm/s, pulsewidth 2ms, frequency 0.0Hz, defocusing amount 2.5mm, spot diameter 0.5mm, argon gas or true
Printed under empty protective atmosphere, individual layer print thickness 0.04mm, the embryo material of acquisition carries out 550 DEG C of annealing, and soaking time 6 is small
When, and electrochemical polish is carried out, polishing fluid is volume ratio 1:3:6 perchloric acid, n-butanol, the mixed liquor of methyl alcohol, using electrochemistry
Work station (IviumStat) is simultaneously provided with the electrolytic cell of agitating device in constant current mode, current density 15A/dm2, temperature -10 takes the photograph
Family name's degree (plus liquid nitrogen cooling), is polished operation under conditions of mixing speed 150r/min, obtain surface roughness on 70 μm of left sides
Right titanium alloy abutment of implant；Absolute alcohol, acetone, deionized water is respectively adopted each ultrasonic cleaning of 15 minutes, is carried out
The de-oiling degreasing on titanium alloy abutment of implant surface, dries at room temperature, obtains the titanium alloy abutment of implant after electrochemical polish.
(6) it is anode by the dried titanium alloy abutment of implant of step (5), stainless steel is negative electrode, in differential arc oxidation liquid
In, it is 600Hz, differential of the arc time 20min in frequency, dutycycle is 20%, and current density is 20A/cm2, operation temperature is 23 DEG C
Under the conditions of carry out differential arc oxidation reaction, after reaction terminates, reacted titanium alloy abutment of implant is taken out, in deionized water
It is cleaned by ultrasonic 15min, is dried in 45 DEG C of baking oven, obtaining surface there are 20 μm of titanium alloy implant bases of differential arc oxidation layer
Body, is designated as titanium alloy abutment of implant/differential arc oxidation film layer, and SEM photograph is as shown in Figure 2；Differential arc oxidation liquid is constituted：10g/L
Na2SiO3、10g/L Na3PO4、8g/L NaOH、5g/L KF、6g/L Na2CO3, 3g/L KOH, 75mL/L absolute ethyl alcohols, solvent
It is deionized water, pH value nature.
(7) electro-deposition is carried out under three-electrode system.With the titanium alloy abutment of implant/differential arc oxidation film layer of step (6)
As working electrode, platinized platinum as to electrode, saturated calomel electrode as reference electrode, in electrochemical deposition liquid, 60 DEG C,
Current density 0.49mA/cm2Under conditions of carry out electrochemical deposition 90min after, by post-depositional matrix take out, use deionized water
Clean, room temperature is dried, be then immersed in the NaOH aqueous solution with 2mol/L, at 80 DEG C to deposition after the deposit phosphoric acid that obtains
Calcium salt soaks 3h, and synthos are fully converted into hydroxyapatite, is then cleaned repeatedly with deionized water, after room temperature is dried,
The high temperature anneal is carried out in tube furnace under argon gas or vacuum protection atmosphere, hydroxyapatite layer and differential arc oxidation is improved
The adhesion of film layer, annealing temperature is 500 DEG C, is incubated 2h, and wherein diamond heating speed is 10 DEG C/min；In micro-arc oxidation films
Layer surface forms 5 μm of hydroxyapatite coating layers being evenly distributed, and is designated as titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyl
Apatite layer, SEM schemes as shown in Figure 3；Electrochemical deposition liquid is constituted：0.042mol/L Ca(NO3)2、0.025mol/L
NH4H2PO4、0.5mol/LNaNO3, 40mL/L absolute ethyl alcohols, hydrogen peroxide 40mL/L, 0.005mol/L APES
OP-21,0.1mol/L trisodium citrate, solvent are deionized water, and pH is 4.
(8) by PLA solid powder, (ten thousand) PLA, weight average molecular weight is added to dichloromethane (DCM for 15:
Dichloromethane in), both are with mass ratio 2.5:97.5 add, and room temperature uniform stirring 6 hours obtains mass concentration
2.5% PLA solution.Step (7) titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer is then immersed in,
After room temperature DEG C immersion 25s, in the presence of Best-Effort request machine (grind science and technology and produce SYDC-100 type Best-Effort requests coating machine in Shanghai three),
Proposed with the constant speed of 20mm/min, room temperature is dried in ventilating kitchen.Then deionized water is cleaned, and room temperature is dried, you can
Obtain surface and sequentially form 25 μm of differential arc oxidation film layers, 5 μm of hydroxyapatite layers, 8 μm of titaniums of polylactic acid layers structure from outside to inside
Alloy is implanted into composite material, is designated as titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer/polylactic acid layers, ties
Structure schematic diagram is as shown in Figure 1.
From figure 2 it can be seen that the micro-arc oxidation films surface obtained by the present embodiment has evenly sized space, it is average empty
Gap is 5~10 μm, and space is evenly distributed, and the pore size is conducive to the apposition growth of bone tissue, promotes bone fusion.
From figure 3, it can be seen that hydroxyapatite product is in shaft-like, partly in cotton-shaped (this implementation hydroxyapatite bar of group
The not exclusive pattern of shape pattern, specific pattern can change because of preparation parameter change), this is due to when differential arc oxidation film layer is by hydroxyl
When base apatite layer is covered, pH value is increased so that caused by the reaction of ensuing hydroxyapatite is more strong (a in Fig. 3), entering
One step is amplified it can be seen that having certain interval between (b in Fig. 3), hydroxyapatite, this is conducive to surface biological macromolecule layer
Prepare, while also further enhancing the biocompatibility of titanium alloy.
2nd, the performance test of titanium alloy abutment of implant
(1) the dynamic polarization test of electrochemistry
(component is 8g/L NaCl, 0.4g/L to titanium alloy implantation composite material prepared by step 1 in Hank solution
KCl, 0.25g/L NaH2PO4·H2O, 0.35g/L NaHCO3,0.06g/L Na2HPO4·2H2O, 0.19g/L MgCl2,
0.19g/L CaCl2·2H2O, 0.06g/L MgSO4·H2O and 1g/L glucose, deionized water prepare, pH 7.8) in carry out
The dynamic polarization test of electrochemistry, it is electrochemical workstation (IviumStat) to use equipment, and its specific test parameter is：Sweep speed
It is 1mVs-1, sweep limits is -2.0V to 1.0V, titanium alloy implantation composite material (titanium alloy/MAO/ prepared by step 1
HAP/PLC) as working electrode, platinum electrode is made to electrode, and saturated calomel electrode is carried out as reference electrode at a temperature of 37 DEG C
Test, is control with titanium alloy abutment of implant (i.e. titanium alloy in table 1) prepared by step (5), and the experimental data for measuring is as follows
Shown in table 1：
The analysis result of polarization curve in table 1.Hank solution
| Sample | Ecorr(V) | |
| Titanium alloy | -1.41 | |
| Titanium alloy/MAO/HAP/PLC | -0.24 |
Can be obtained by table 1, the corrosion potential of titanium alloy implantation composite material prepared by present case is from being not handled by
- 0.24V is arrived in preceding -1.41V liftings.In general, a corrosion potential higher shows that it has more preferable decay resistance,
Therefore, the titanium alloy implantation composite material that prepared by present case has been obviously improved the decay resistance of Titanium base.From corrosion current
Density can be seen that the corrosion electric current density of the matrix after treatment reduces 2~3 orders of magnitude, and this shows titanium prepared by present case
Alloy implantation composite material significantly reduces the corrosion rate of matrix.Dynamic polarization test results can illustrate, the titanium of preparation
Alloy implantation composite material can effectively improve the decay resistance of titanium alloy substrate.
(2) attachment Gegenbaur's cell experiment
The titanium alloy implantation composite material prepared to step 1 carries out external osteoblasts cultivation experiment：Will be from adult rabbits
The Gegenbaur's cell for obtaining in vivo is cleaned twice with pH=7.5 phosphate buffers, is centrifuged, and collects cell precipitation, and cell precipitation is connect
Plant into DMEM nutrient solutions, in 5%CO2, to be cultivated 1 week at 37 DEG C, cell precipitation pH=7.5 phosphate buffers are collected in centrifugation
It is configured to 5 × 105/ ml Gegenbaur's cell suspensions.Titanium prepared by titanium alloy abutment of implant and step (8) prepared by step (5)
Alloy implantation composite material is sterilized 40 minutes in 110 DEG C of water vapours, and the sample of 10mm × 10mm × 1mm sizes is then taken respectively
Product are added in six orifice plates, add 5 × 105/ the ml Gegenbaur's cell suspension 1ml and DMEM containing 10% hyclone (FBS) are trained
Nutrient solution 10ml, 5%CO2, 37 DEG C of culture 24h remove for three times unattached thin with pH=7.5 phosphate buffer solutions board-washings afterwards
Born of the same parents, are subsequently adding 0.5ml digestive juices (pancreas enzyme -EDTA) digestion, and the standard digestive juice (pancreatin inhibitor) for adding 0.5ml terminates
Digestion, is made cell suspension, and cell count is carried out with Z2 type cellular granularity calculating instruments.Its count results is as shown in table 2 below：
The cell count of each group after the culture in 24 hours of 2. Gegenbaur's cell of table
| Sample | Attached cell number |
| Titanium alloy | 40000±2000 |
| Titanium alloy/MAO/HAP/PLC | 53000±1000 |
The Ti/MAO/HAP/PLC composite coating materials as obtained in table 2 can obtain present case have more attachment skeletonization thin
Born of the same parents, this titanium alloy/MAO/HAP/PLC composite coating material for showing to prepare has preferably promotion bone cell growth ability, has
Improve to effect the bioactivity of Titanium base material.
Embodiment 2
Step (1)~(4) are identical with the condition in embodiment 1；
Laser power in the step of embodiment 1 (5) is changed to 250W, sweep speed 1300mm/s by step (5), annealing temperature
Degree is changed to 700 DEG C, soaking time 7 hours；
Be changed to for differential arc oxidation liquid composition in the step of embodiment 1 (6) by step (6)：8g/L Na2SiO3、10g/L
Na3PO4、8g/L NaOH、3g/L KF、3g/L Na2CO3, 1g/L KOH, 50mL/L absolute ethyl alcohols, solvent is deionized water, pH
Value nature.The control parameter of differential arc oxidation is changed to：Frequency is 550Hz, and the differential of the arc time is 15min, and dutycycle is 15%, and electric current is close
It is 15A/cm to spend2, remaining condition is constant；Titanium alloy abutment of implant/differential arc oxidation film layer is obtained, contact angle figure is as shown in Figure 4.
Be changed to for electrochemical deposition liquid composition in the step of embodiment 1 (7) by step (7)：0.042mol/L Ca(NO3)2、
0.025mol/L NH4H2PO4、0.5mol/L NaNO3, 30mL/L absolute ethyl alcohols, 30mL/L hydrogen peroxide, 0.004mol/L alkyl
Phenol polyethenoxy ether OP-21,0.0008mol/L NaF, 0.2mol/L trisodium citrate, solvent is deionized water, uses slow hematic acid
Amine and nitre acid for adjusting pH are 3, and electrochemical deposition condition is changed to：Constant current mode, current density is 0.39mA/cm2, depositing temperature is
50 DEG C, sedimentation time is 60min, and remaining condition is constant.The concentration of NaOH is changed to 1mol/L, and soak time is changed to 2h, remaining
Part is constant；Titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer is obtained, as shown in Figure 4, SEM shines contact angle figure
As shown in Figure 5, XRD spectra is as shown in Figure 6 for piece.
Soak time in the step of embodiment 1 (8) is changed to 20s by step (8), and lifting speed is changed to the perseverance of 15mm/min
Constant speed degree, remaining condition is constant, obtains titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer/polylactic acid layers knot
The titanium alloy implant composite material of structure, differential arc oxidation film layer thickness is 20 μm, and hydroxyapatite layer thickness is 3 μ
M, polylactic acid layers thickness is 5 μm.
Figure 4, it is seen that the micro-arc oxidation films surface contact angle obtained by the present embodiment is 87 ° (a in Fig. 4), and enter
After the deposition of row fluorine hydroxyapatite, it is 35.8 ° (b in Fig. 4) that contact angle is significantly reduced, and this shows deposition layer tool of the invention
There is excellent hydrophily, may advantageously facilitate absorption of the albumin on surface so that it can occur more with extracellular matrix protein
Good exchange, promotes the adhesion of bone and its cells.
From figure 5 it can be seen that fluorine hydroxyapatite product prepared by electro-deposition is in nanoscale acicular texture, can after amplification
See obvious flower-like structure, this is, because differential arc oxidation hole increases surface area, to promote the nucleation rate of matrix surface,
A lower crystallite dimension is result in, and low crystallite dimension is more beneficial for improving the bioactivity of material, enhances titanium conjunction
The biocompatibility of gold.Meanwhile, it can clearly be seen that differential arc oxidation hole after deposit cover to a certain extent, obtain covering equal
Even surface.
Fig. 6 is that the present embodiment gained titanium alloy substrate carries out the XRD after differential arc oxidation and electrochemical fluorine hydroxyapatite
Spectrogram, there are hydroxyapatite, fluorine hydroxyapatite and differential arc oxidation layer titanium dioxide peak composition in surface after collection of illustrative plates shows electro-deposition,
And matrix is well covered, obvious matrix peak is had no.
Embodiment 3
Step (1)~(4) are identical with the condition in embodiment 1；
Laser power in the step of embodiment 1 (5) is changed to 250W, sweep speed 1500mm/s by step (5), annealing temperature
Degree is changed to 800 DEG C, soaking time 8 hours；
Be changed to for differential arc oxidation liquid composition in the step of embodiment 1 (6) by step (6)：12g/L Na2SiO3、12g/
LNa3PO4、10g/L NaOH、7g/L KF、8g/L Na2CO3, 5g/L KOH, 100mL/L absolute ethyl alcohols, solvent is deionization
Water, pH value nature.The control parameter of differential arc oxidation is changed to：Frequency is 650Hz, and the differential of the arc time is 30min, and dutycycle is 30%,
Current density is 25A/cm2, and remaining condition is constant；
Be changed to for electrochemical deposition liquid composition in the step of embodiment 1 (7) by step (7)：0.042mol/L Ca(NO3)2、
0.025mol/L NH4H2PO4、0.5mol/L NaNO3, 50mL/L absolute ethyl alcohols, 50mL/L hydrogen peroxide, 0.006mol/L alkyl
Phenol polyethenoxy ether OP-21,0.0008mol/L NaF, 0.15mol/L trisodium citrate, solvent is deionized water, uses slow hematic acid
Amine and nitre acid for adjusting pH are 5, and electrochemical deposition condition is changed to：Constant current mode, current density is 0.59mA/cm2, depositing temperature is
70 DEG C, sedimentation time is 120min.The concentration of NaOH is changed to 2mol/L, and soak time is changed to 4h, and remaining condition is constant.
Soak time in the step of embodiment 1 (8) is changed to 30s by step (8), and lifting speed is changed to the perseverance of 25mm/min
Constant speed degree, remaining condition is constant.Obtain titanium alloy abutment of implant/differential arc oxidation film layer/hydroxyapatite layer/polylactic acid layers knot
The titanium alloy implant composite material of structure, differential arc oxidation film layer thickness is 30 μm, and hydroxyapatite layer thickness is 5 μ
M, polylactic acid layers thickness is 10 μm.
Claims (10)
1. a kind of titanium alloy is implanted into composite material, it is characterised in that the titanium alloy implantation composite material is passed through with Titanium Powder
The model that 3D printing makes is titanium alloy abutment of implant, forms micro- using micro-arc oxidation on titanium alloy abutment of implant surface
Arc oxidation film layer, then forms hydroxyapatite layer or fluorine hydroxyl phosphorus in micro-arc oxidation films layer surface using electrochemical deposition method again
Grey rock layers, finally form polylactic acid layers in hydroxyapatite layer or fluorine hydroxyapatite layer surface impregnation；The micro-arc oxidation
Differential arc oxidation liquid used is constituted：8~12g/L Na2SiO3, 8~12g/L Na3PO4, 6~10g/L NaOH, 3~7g/L
KF, 3~8g/L Na2CO3, 1~5g/L KOH, 50~100mL/L absolute ethyl alcohols, solvent is deionized water, pH value nature；It is described
Electrochemical deposition liquid composition is used by hydroxyapatite layer：0.042mol/L Ca(NO3)2、0.5mol/L NaNO3、
0.025mol/L NH4H2PO4, 30-50mL/L absolute ethyl alcohols, 30-50mL/L hydrogen peroxide, 0.004-0.006mol/L alkyl phenols gather
Oxygen vinethene OP-21,0.1-0.2mol/L trisodium citrate, solvent is deionized water, is with trometamol and nitre acid for adjusting pH
3-5；The fluorine hydroxyapatite layer electrochemical deposition liquid is to be added in electrochemical deposition liquid used by hydroxyapatite layer
0.0008mol/L NaF。
2. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the differential arc oxidation film layer thickness is 20 μ
M~30 μm, the hydroxyapatite layer or fluorine hydroxyapatite layer thickness are 3 μm~5 μm.
3. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the differential arc oxidation film layer is by such as lower section
It is prepared by method：With described titanium alloy abutment of implant as anode, stainless steel is negative electrode, is 550 in frequency in differential arc oxidation liquid
~650Hz, the differential of the arc time is 15~30min, and dutycycle is 15~30%, and current density is 15-25A/cm2, operation temperature is
Differential arc oxidation reaction is carried out under room temperature condition, reaction is taken out titanium alloy substrate, is cleaned by ultrasonic in deionized water after terminating,
Dried in 20-45 DEG C of baking oven, obtain the titanium alloy abutment of implant that surface forms differential arc oxidation film layer.
4. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the hydroxyapatite layer is by such as lower section
It is prepared by method：The titanium alloy abutment of implant of differential arc oxidation film layer is formed as working electrode with surface, platinized platinum is used as to electrode, saturation
Used as reference electrode, in electrochemical deposition liquid, constant current mode, current density is 0.39~0.59mA/cm to calomel electrode2, sink
After accumulated temperature degree under conditions of 50-70 DEG C to carry out electrochemical deposition 60-120min, described titanium alloy abutment of implant is taken
Go out, be washed with deionized water only, room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L, 2-4h is soaked at 80 DEG C, then
Cleaned repeatedly with deionized water, after room temperature is dried, carry out high annealing in tube furnace under argon gas or vacuum protection atmosphere
Treatment, 500 DEG C are warming up to the speed of 10 DEG C/min, are incubated 2h, are obtained surface and are sequentially formed hydroxyapatite layer from outside to inside
Or the titanium alloy abutment of implant of fluorine hydroxyapatite layer and micro-arc oxidation films Rotating fields.
5. titanium alloy as claimed in claim 1 implantation composite material, it is characterised in that the thickness of the polylactic acid layers is 5 μm~
10μm。
6. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the polylactic acid layers are made as follows
It is standby：PLA is added in dichloromethane, room temperature uniform stirring 6 hours, obtains the PLA solution of mass concentration 2.5%；Will
Surface sequentially forms hydroxyapatite layer or fluorine hydroxyapatite layer, the titanium alloy implant base of differential arc oxidation film layer from outside to inside
In body immersion PLA solution, after soaking at room temperature 20-30s, proposed with the constant speed of 15-25mm/min, in ventilating kitchen interior room
Temperature is dried, and then deionized water is cleaned, and room temperature is dried, that is, obtain surface and sequentially form polylactic acid layers, hydroxy-apatite from outside to inside
Rock layers or fluorine hydroxyapatite layer, the titanium alloy implantation composite material of differential arc oxidation film layer.
7. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the titanium alloy abutment of implant is by such as
It is prepared by lower section method：(1) impaired bone structure is carried out into CT scan, obtains the CT scan data of impaired bone structure, and be input to
Materialise 3 d modeling softwares, carry out threshold value division, and the noise for importing image is then removed using region growth method, enter
The removal of row redundant data, segmentation both injured bones structural region；(2) obtained by Materialise 3 d modeling softwares opening operation
The three-dimensional structure data of impaired bone structure, the three-dimensional structure data that then will be obtained is input into UG softwares, obtains digitlization Cranial defect
Threedimensional model；(3) according to digitlization Cranial defect threedimensional model, Cranial defect module is designed using CAD software, obtains STL models；
(4) titanium alloy powder is well mixed in ball mill, mill rotating speed is 250r/min, and Ball-milling Time is 30min, and uses nitrogen
Gas obtains the titanium alloy powder after ball milling as protective gas；By STL mode input 3D printers, and the titanium after ball milling is closed
Bronze end adds 3D printer, is molded using laser 3D printing, and the power of laser is 200~300W, and sweep speed 1200~
1500mm/s, 1~3ms of pulsewidth, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.5mm, argon gas or vacuum protection atmosphere
Lower printing, individual layer print thickness 0.04mm, the embryo material of acquisition carries out electrochemical polish after being incubated 6-8h at 550-800 DEG C, polishes
Liquid is volume ratio 1:3:6 perchloric acid, n-butanol and methyl alcohol mixed liquor, using electrochemical workstation and the electricity equipped with agitating device
Solution groove is in constant current mode, 10~20A/dm of current density2, -30 DEG C, thrown under conditions of 100~200r/min of mixing speed
Light is operated, then successively with the ultrasonic cleaning of absolute alcohol, acetone and deionized water, drying at room temperature, the described titanium alloy implantation of acquisition
Body matrix.
8. titanium alloy as claimed in claim 1 is implanted into composite material, it is characterised in that the Titanium Powder is Ti-6Al-4V titaniums
Alloy powder, particle diameter is 100 μm~120 μm.
9. titanium alloy described in a kind of claim 1 is implanted into the preparation method of composite material, it is characterised in that methods described is：
(1) impaired bone structure is carried out into CT scan, obtains the CT scan data of impaired bone structure, and it is three-dimensional to be input to Materialise
Modeling software, carries out threshold value division, and the noise for importing image is then removed using region growth method, carries out going for redundant data
Except, segmentation both injured bones structural region；(2) the three of impaired bone structure are obtained by Materialise 3 d modeling softwares opening operation
Dimension structured data, the three-dimensional structure data that then will be obtained is input into UG softwares, obtains digitlization Cranial defect threedimensional model；(3) root
According to digitlization Cranial defect threedimensional model, Cranial defect module is designed using CAD software, obtain STL models；(4) by titanium alloy powder
It is well mixed in ball mill, mill rotating speed is 250r/min, and Ball-milling Time is 30min, and it is protective gas to employ nitrogen as,
Obtain the titanium alloy powder after ball milling；By STL mode input 3D printing equipment, and the titanium alloy powder after ball milling is placed in 3D beats
In printing apparatus, it is molded using laser 3D printing, the power of laser is 200~300W, 1200~1500mm/s of sweep speed, pulsewidth
1~3ms, frequency 0.0Hz, 2~3mm of defocusing amount, spot diameter 0.5mm, print under argon gas or vacuum protection atmosphere, and individual layer is beaten
Print thickness 0.04mm, the embryo material of acquisition carries out electrochemical polish after being incubated 6-8h at 550-800 DEG C, polishing fluid is volume ratio 1:3:
6 perchloric acid, n-butanol and methyl alcohol mixed liquor, using electrochemical workstation and the electrolytic cell equipped with agitating device is in constant current mould
Formula, 10~20A/dm of current density2, -30 DEG C, operation is polished under conditions of 100~200r/min of mixing speed, then successively
It is cleaned by ultrasonic with absolute alcohol, acetone and deionized water, is dried at room temperature, obtains described titanium alloy abutment of implant；(5) with
Described titanium alloy abutment of implant is anode, and stainless steel is negative electrode, and in differential arc oxidation liquid, frequency is 550~650Hz, micro-
The arc time is 15~30min, and dutycycle is 15~30%, and current density is 15-25A/cm2, operation temperature is under room temperature condition
Differential arc oxidation reaction is carried out, reaction is taken out described titanium alloy abutment of implant, is cleaned by ultrasonic in deionized water after terminating,
Dried in 20-45 DEG C of baking oven, obtain the titanium alloy implant that surface forms differential arc oxidation film layer, be designated as titanium alloy implant base
Body/differential arc oxidation film layer；(6) with step (5) titanium alloy abutment of implant/differential arc oxidation film layer as working electrode, platinized platinum conduct
To electrode, used as reference electrode, in electrochemical deposition liquid, constant current mode, current density is 4-6mA/ to saturated calomel electrode
cm2, after depositing temperature under conditions of 37 DEG C to carry out electrochemical deposition 90-150min, by described titanium alloy abutment of implant
Take out, be washed with deionized water only, room temperature is dried；Immerse again in the NaOH aqueous solution of 1-2mol/L, 2-4h is soaked at 80 DEG C, so
Cleaned repeatedly with deionized water afterwards, after room temperature is dried, under argon gas or vacuum protection atmosphere carrying out high temperature in tube furnace moves back
Fire treatment, 200 DEG C are warming up to the speed of 10 DEG C/min, are incubated 2h, are obtained surface and are sequentially formed micro-arc oxidation films from the inside to the outside
The titanium alloy abutment of implant of layer, hydroxyapatite layer or fluorine hydroxyapatite Rotating fields, is designated as titanium alloy abutment of implant/micro-
Arc oxidation film layer/hydroxyapatite layer or fluorine hydroxyapatite layer；(7) PLA is added in dichloromethane, room temperature is uniform
Stirring 6 hours, obtains the PLA solution of mass concentration 2.5%；By step (7) titanium alloy abutment of implant/differential arc oxidation film layer/
In hydroxyapatite layer or fluorine hydroxyapatite layer immersion PLA solution, after soaking at room temperature 20-30s, with 15-25mm/min's
Constant speed proposes that room temperature is dried in ventilating kitchen, and then deionized water is cleaned, and room temperature is dried, that is, obtain surface from outside to inside
Sequentially form the titanium alloy implantation bluk recombination of polylactic acid layers, hydroxyapatite layer or fluorine hydroxyapatite layer, differential arc oxidation film layer
Material.
10. application of the titanium alloy implantation composite material in bone renovating material is prepared described in a kind of claim 1.
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| CN111922340A (en) * | 2020-06-30 | 2020-11-13 | 吉林大学 | Method for preparing medical titanium alloy material by laser sintering |
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