CN108079381A - A kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating - Google Patents

A kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating Download PDF

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CN108079381A
CN108079381A CN201711329754.1A CN201711329754A CN108079381A CN 108079381 A CN108079381 A CN 108079381A CN 201711329754 A CN201711329754 A CN 201711329754A CN 108079381 A CN108079381 A CN 108079381A
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coating
titanium alloy
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medical
biological piezoelectric
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CN108079381B (en
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汤玉斐
田朴
赵康
吴聪
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Xian University of Technology
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    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/10Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
    • A61L2300/40Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
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    • A61L2300/00Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
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    • A61L2430/00Materials or treatment for tissue regeneration
    • A61L2430/02Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Abstract

The invention discloses a kind of preparation methods of medical titanium alloy surface biological Piezoelectric anisotropy coating, first using differential arc oxidization technique in the porous coating of titanium dioxide in titanium alloy substrate surface in situ generation inner compact layer, surface layer, then barium titanate coating is generated in coating of titanium dioxide reaction in-situ using hydrothermal chemistry method, the hole of coating surface after finally filling polarization forms the composite coating with biological piezoelectric property on medical titanium alloy surface.Coating inner compact layer produced by the present invention, is well combined with matrix, and stability is high, while harmful metal ion can effectively be prevented to be dissolved out to body fluid;The porous barium titanate coating in surface layer can generate piezoelectric effect, promote local blood circulation, further speed up the reparation of bone;The substance or antimicrobial DP finish of the growth beneficial to early stage bone tissue are filled in hole, while coarse surface is beneficial to the adherency and increment of cell so that metal material has good biocompatibility and bioactivity.

Description

A kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating
Technical field
The invention belongs to biomedical material surface technical field of modification, are related to a kind of medical titanium alloy surface biological piezoelectricity The preparation method of composite coating.
Background technology
Medical titanium alloy is because of itself high intensity, low elastic modulus, nonmagnetic, excellent chemical stability and good life Object compatibility and be widely used in medical embedded field.But medical titanium alloy is deposited in ingredient and configuration aspects and bone tissue In larger difference, it is simple mechanical interlock to be implanted into after human body between bone tissue, it is impossible to strong chemical bonding is formed, The loosening of implant is be easy to cause with coming off.Therefore surface modification is carried out to it to be necessary, and surface modification can be protected The problems such as staying the excellent properties of titanium alloy in itself, and the bioactivity that it is lacked can be solved.
Research shows that bone tissue is natural piezoelectrics, can this kind of small mechanical stress of displacement be converted into electricity Effect generates micro-current.Micro-current acts on calcium ion, phosphate anion in human body fluid, promotes its deposition, is bone tissue Growth provide nutrient, improve the integration to host's bone implant material, while this electric signal acts on osteocyte and cell External environment promotes the generation of extracellular space macromolecular, and bone living is further made to accelerate healing.At present, as in bone renovating material Based on being studied with piezoelectric ceramics, and leadless piezoelectric ceramics barium titanate (BaTiO3), good piezoelectricity and biocompatibility and It is widely studied.Therefore, it is excellent to study a kind of piezoelectric property, bioactivity is high, and coating is strong with basal body binding force, while coating is steady Qualitative good biological Piezoelectric anisotropy coating is the hot and difficult issue that biomedical material surface is modified field.
Chinese patent《A kind of preparation method of titanium alloy substrate hydroxyapatite coating on surface》(the applying date 2014.11.14, publication number CN105018924A, publication date 2015.11.04) disclose a kind of titanium alloy substrate surface hydroxyl phosphorus The preparation method of lime stone coating is that mixed titanium powder and hydroxyapatite powder are sprayed into titanium using cold spray technique to close Then golden matrix surface prepares hydroxyapatite coating layer using laser melting and coating technique in titanium alloy substrate surface.The coating is main New born formation is induced by hydroxyapatite to improve the bioactivity of titanium alloy surface, but hydroxyapatite is implanted into for a long time It can gradually degrade after human body, film layer comes off, and bioactivity continuously decreases.
Chinese patent《Active bio piezoelectric ceramic coating and the method for preparing the coating on Titanium base surface》(the applying date 2005.10.14, publication number CN1785439A, publication date 2006.06.14) a kind of method of titanium material surface modifying is disclosed, Porous oxide membranous layer is mainly formed by differential arc oxidization technique, then by electrophoretic deposition technique, is prepared in sample surfaces Fluorine hydroxyapatite and barium titanate (FHABT) composite coating improve its biocompatibility and bioactivity.But fluorine hydroxyl in coating After the degradation of base apatite, since barium titanate particles can not degrade in human body, it may dissociate in human body, human body can be caused Potential damage, while it is poor to combine power between the film layer of electrophoretic deposition and the oxide membranous layer of differential arc oxidation formation.
Chinese patent《The lye steam post-processing approach of titanium surface by micro-arc oxidation bioactivity coatings》(the applying date 2013.07.18, publication number CN103334144A, publication date 2013.10.02) disclose a kind of side of titanium material surface modifying Method, progress differential arc oxidation forms oxide membranous layer on Titanium base surface mainly in the mixed electrolytic solution containing calcium microcosmic salt, after Biologically active coating is prepared on titanium surface by lye Steam treatment.The coating handles to avoid by alkali hot water vapor Conventional hydrothermal chemical method causes the dissolution of biological active elements, and generates the problem of apatite is less.But coating biology activity Substance is still apatite, and after degradation completely, the activity of matrix decreases, coating stability deficiency.
Chinese patent《A kind of metallic surface structures gradient biological coating and its preparation method and application》(the applying date 2004.01.16, publication number CN1557505A, publication date 2004.12.29) disclose a kind of metallic surface structures gradient biology painting Layer and its preparation method and application, this method first form fine and close pure anatase titanium dioxide in matrix surface with anodic oxidation Film, then with differential arc oxidation in dense oxidation film Surface Creation calcic, the porous pure Detitanium-ore-type of phosphorus or anatase and gold Red stone mixed type coating of titanium dioxide.Coated substrate is titanium or titanium alloy, and structure feature is that " inner compact layer+surface layer convex-concave is not It is flat porous " gradient-structure.But the coating active material is mainly calcium, P elements in coating, and bioactivity is insufficient.
The paper that S.Hwangbo etc. is delivered《In-vitro calcium phosphate formation on electrostatic sprayed–perovskite BaTiO3layer on Ti implant after poling treatment》, it is selected from《Ceramics International》The 2nd the 2462-2466 pages of the phase of volume 41 in 2015, in titanium table Face barium titanate coating is prepared by Electrostatic Spray Technology.But the coating and basal body binding force deficiency, it is impossible to meet clinical needs.
The paper that Ho-Jun Song etc. are delivered《Fabrication of BaTiO3films on titanium by microarc oxidation method and improvement of bioactivity by electric poling treatment》, it is selected from《Materials Letters》The 16th the 3473-3476 pages of the phase of volume 61 in 2007, lead on titanium surface It crosses differential arc oxidization technique and prepares barium titanate coating.But piezoelectricity phase barium titanate content is relatively low in the coating, and piezoelectric property is not high, together When coating in bioactive substance it is less, bioactivity deficiency.
The content of the invention
The object of the present invention is to provide a kind of preparation methods of medical titanium alloy surface biological Piezoelectric anisotropy coating, solve The problem of bioactivity coatings prepared by existing method are poor with basal body binding force, and surface bioactive is low.
The technical solution adopted in the present invention is a kind of preparation side of medical titanium alloy surface biological Piezoelectric anisotropy coating Method is applied first using the differential arc oxidization technique titanium dioxide porous on titanium alloy substrate surface in situ generation inner compact layer, surface layer Then layer makes coating of titanium dioxide reaction in-situ generate barium titanate coating using hydrothermal chemistry method, the painting after finally filling polarization The hole of layer surface forms the composite coating with biological piezoelectric property on medical titanium alloy surface.
The features of the present invention also resides in,
Coating of titanium dioxide is rich in Ca, P element.
Specifically implement according to following steps:
Step 1, it will be placed in the stainless steel trough body containing electrolyte by the titanium alloy substrate sample of pretreatment, closed with titanium Auri body sample is anode, and stainless steel trough body is cathode, raw in situ in titanium alloy substrate specimen surface using differential arc oxidization technique The coating of titanium dioxide porous into inner compact layer, surface layer;
Step 2, baryta water is added in a kettle, by step 1 differential arc oxidation treated titanium alloy substrate Sample, which is placed in reaction kettle, carries out hydro-thermal reaction, and barium titanate coating is generated in coating of titanium dioxide surface in situ;
Step 3, the titanium alloy substrate sample handled through step 2 is polarised;
Step 4, the hole on the titanium alloy substrate sample coatings surface after wadding warp step 3 polarization process, i.e., in titanium alloy Surface obtains the composite coating with biological piezoelectric property.
It containing complexing agent concentration is 0.05-0.2mol/L that electrolyte, which is, in step 1, calcium ion concentration 0.01-0.5mol/ L, phosphorus acid ion concentration be 0.05-0.5mol/L mixed aqueous solution.
Complexing agent is citric acid, one kind in disodium ethylene diamine tetraacetate or mixing;Calcium ion source is in for calcium acetate, nitre Sour calcium, calcium chloride;Phosphate anion is from sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, β-glycerine phosphorus One or more of sour sodium or β-potassium glycerinophosphate.
Differential arc oxidation parameter is in step 1:Differential arc oxidation uses pulsed dc voltage, voltage 200-500V, pulse frequency Rate is 300-900Hz, and duty cycle 10-50%, electrolyte temperature is less than 60 DEG C, oxidization time 4-20min.
Baryta water concentration is 0.1mol/L-0.3mol/L in step 2, and addition is reaction kettle total volume 50%-70%;Hydrothermal temperature is 140-220 DEG C, keeps the temperature 6-16h.
Polarized media is any one in air, methyl-silicone oil, transformer oil in step 3;Polarizing voltage is 1-5kV, Poling temperature is 30-150 DEG C, polarization time 1-5h.
The material that hole is filled in step 4 is bioactive substance or anti-microbial type substance.
Fill method is infusion process or nanometer air spray finishing in step 4.
The invention has the advantages that the present invention is reacted first using differential arc oxidization technique in medical titanium alloy surface in situ It forms inner compact layer to be firmly combined with, the oxide layer of porous surface, on this basis, using hydrothermal chemistry method by porous oxide layer Reaction in-situ generates barium titanate coating, by polarization process, composite coating is made to have piezoelectric property, finally using dipping, spraying The substance for promoting cell growth is filled in hole by the technologies such as method, and on medical titanium alloy surface, " inner compact layer+surface layer is more for formation Fill out object in hole+hole " the coating structure with biological piezoelectric property.Coating inner compact layer, is well combined with matrix, stability Height, while harmful metal ion can effectively be prevented to be dissolved out to body fluid;The porous bionical people of its piezoelectricity of barium titanate coating in surface layer The power for being applied to bone tissue can be reached material and generate piezoelectric effect by the piezoelectric effect of body bone by human body own activity, Suitable electro photoluminescence can improve the deposition of hydroxyapatite, promote local blood circulation, further speed up the reparation of bone;Hole In be filled with the life that calcium phosphate bone cement, hydroxyapatite, Argent grain, gentamicin, chitosan etc. are conducive to early stage bone tissue Long substance or antimicrobial DP finish, while coarse surface is beneficial to the adherency and increment of cell so that metal material has good Biocompatibility and bioactivity.
Description of the drawings
Fig. 1 is that step 1 of the present invention prepares inner compact layer, the coating of titanium dioxide of porous surface on titanium alloy substrate surface Structure diagram;
Fig. 2 is the biological Piezoelectric anisotropy coating structure schematic diagram having that the present invention is prepared.
In figure, 1. titanium alloy substrates, 2. porous oxide coatings, 3. bioactive substances.
Specific embodiment
The present invention is described in detail with reference to the accompanying drawings and detailed description.
The present invention provides a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating, first using the differential of the arc Oxidation technology is in matrix surface in-situ preparation rich in the porous coating of titanium dioxide in Ca, P element, inner compact layer, surface layer;Then it is sharp With hydrothermal chemistry method, under alkali heat condition, barium ions is made to enter in coating of titanium dioxide, barium ions and titanium dioxide reaction in-situ Generate barium titanate coating;The hole of coating surface after finally filling polarization, having obtained a kind of surface has biological piezoelectric property Composite coating.
Specifically implement according to the following steps:
Step 1, titanium alloy substrate surface by micro-arc oxidation prepares coating of titanium dioxide
It will be placed in by the titanium alloy substrate sample of pretreatment in the stainless steel trough body containing electrolyte, using titanium sample as sun Pole, stainless steel trough body are cathode, carry out differential arc oxidation processing, differential arc oxidation use pulsed dc voltage, voltage 200-500V, Pulse frequency is 300-900Hz, and duty cycle 10-50%, electrolyte temperature is less than 60 DEG C, and oxidization time 4-20min is obtained The porous coating of titanium dioxide in inner compact layer, surface layer, as shown in Figure 1.
It containing complexing agent concentration is 0.05-0.2mol/L that electrolyte, which is, calcium ion concentration is 0.01-0.5mol/L, phosphorus Acid ion concentration is the mixed aqueous solution of 0.05-0.5mol/L.The electrolyte of calcium ion is provided as calcium acetate, calcium nitrate, chlorine Change calcium;The electrolyte of phosphate anion is provided as sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, β-glycerine phosphorus Sour sodium or β-potassium glycerinophosphate;Complexing agent is citric acid, one kind in disodium ethylene diamine tetraacetate or mixing.
Step 2, barium titanate coating is prepared in situ in hydro-thermal method
The hydrogen-oxygen for accounting for the concentration of reaction kettle total volume 50%-70% as 0.1mol/L-0.3mol/L is added in into reaction kettle Change barium aqueous solution, by step 1 differential arc oxidation, treated that titanium sample is positioned in hydrothermal reaction kettle, at a temperature of 140-220 DEG C, 6-16h is kept the temperature, i.e., generates barium titanate coating in coating of titanium dioxide surface in situ.
In hydrothermal reaction process, the barium ions in hydrothermal solution enters in coating of titanium dioxide, under alkali heat condition, barium from Son chemically reacts in situ with titanium dioxide, so as to generate barium titanate coating.
Step 3, polarization process
The titanium alloy sample that step 2 obtains is polarized in media as well, polarizing voltage 1-5kV, poling temperature 30- 150 DEG C, polarization time 1-5h;Sample is taken out after the completion of polarization, is cleaned by ultrasonic successively with absolute ethyl alcohol, deionized water 10min, drying.
Medium is any one in air, methyl-silicone oil, transformer oil.
Step 4, filling perforation is handled
Using infusion process or nanometer air spray finishing, to the titanium alloy sample coatings surface after step 3 polarization process Holes filling contributes to bone or the substance of cell growth to get having the composite coating of biological piezoelectric property to surface, such as Shown in Fig. 2.
Bone or the substance of cell growth is contributed to include bioactive substance and anti-microbial type substance.Wherein bioactivity Substance is hydroxyapatite (HA), calcium phosphate bone cement etc.;Anti-microbial type substance includes nano silver, chitosan, gentamicin etc..
Infusion process is filled, and is specially:
Substance to be filled is formulated as aqueous solution, the titanium alloy sample after polarization process is immersed in solution and is sufficiently impregnated, It takes out and air-dries, above operation, repetitive operation number >=5, until being filled up in hole are repeated several times.
Nanometer air spray finishing filling, specially:It is cleaned by ultrasonic sample with absolute ethyl alcohol first, then drying utilizes height Pressure air does not inhale the titanium alloy specimen surface that with filler particle is sprayed on polarization process after of the grain size less than 10 μm with one piece The burnishing surface rapid application of water bubble is uniform, is gently polished with clean and dry soft superfine fibre cloth;Then nothing is used again Water-ethanol wipe samples surface is once, repeated multiple times to repeat spraying operation, repetitive operation number >=5, until having filling in hole Object powder exists, and vapor then is sprayed on sample surfaces, sprays 5min-30min.
What the method for the present invention formd " inner compact layer+surface layer is porous+hole in fill out object " in medical titanium alloy has biology pressure The coating structure of electrical property.Coating inner compact layer, is well combined with matrix, and stability is high, while can effectively prevent harmful gold Belong to ion to dissolve out to body fluid;The piezoelectric effect of the porous bionical human body bone of its piezoelectricity of barium titanate coating in surface layer, can rely on people The power for being applied to bone tissue is reached material and generates piezoelectric effect by body own activity, and suitable electro photoluminescence can improve hydroxyl phosphorus The deposition of lime stone promotes local blood circulation, further speeds up the reparation of bone;Be filled in hole calcium phosphate, hydroxyapatite, It carries silver, carry the substance that medicine etc. is conducive to the growth of early stage bone tissue, while coarse surface is beneficial to the adherency and increment of cell, makes Obtaining metal material has good biocompatibility and bioactivity.
Embodiment 1
The Titanium base sample of pretreatment is placed in the stainless steel trough body containing electrolyte, it is stainless using titanium sample as anode Steel tank body is cathode, using pulsed dc voltage, voltage 200V, pulse frequency 700Hz, duty cycle 10%, oxidization time 4min, electrolyte temperature are 60 DEG C.Electrolyte be by solvent be deionized water, solute is the ethylenediamine that concentration is 0.05mol/L The sodium dihydrogen phosphate that calcium acetate that tetraacethyl disodium, concentration are 0.01mol/L, concentration are 0.05mol/L mixes;
The baryta water for accounting for the concentration of reaction kettle total volume 50% as 0.1mol/L is added in into reaction kettle, it will be micro- Titanium sample after arc oxidation processes is positioned in hydrothermal reaction kettle, then at a temperature of 140 DEG C, keeps the temperature 6h;
By above-mentioned steps, treated that sample is polarised in air medium, polarizing voltage 1kV, and temperature is 150 DEG C, time 1h takes out sample after the completion of polarization, is cleaned by ultrasonic 10min successively with absolute ethyl alcohol, deionized water, dries It is dry;
A certain amount of simulated body fluid (SBF) is prepared, the coating surface of sample with SBF liquid levels is just contacted, utilizes liquid Capillary force action makes SBF liquid enter in coating surface hole, keeps 10min, takes out sample, and natural air drying is repeated 5 times State operation.The composite coating with biological piezoelectric property can be prepared on medical titanium alloy surface.
Embodiment 2
The Titanium base sample of pretreatment is placed in the stainless steel trough body containing electrolyte, it is stainless using titanium sample as anode Steel tank body is cathode, using pulsed dc voltage, voltage 500V, pulse frequency 300Hz, duty cycle 20%, oxidization time 8min, electrolyte temperature are 60 DEG C.Electrolyte be by solvent be deionized water, solute is the ethylenediamine tetraacetic that concentration is 0.1mol/L The sodium dihydrogen phosphate that calcium acetate that acetic acid disodium, concentration are 0.1mol/L, concentration are 0.07mol/L mixes;
The baryta water for accounting for the concentration of reaction kettle total volume 70% as 0.2mol/L is added in into reaction kettle, it will be micro- Titanium sample after arc oxidation processes is positioned in hydrothermal reaction kettle, then at a temperature of 180 DEG C, keeps the temperature 8h;
By above-mentioned steps, treated that sample is polarised in air medium, polarizing voltage 3kV, and temperature is 100 DEG C, time 3h takes out sample after the completion of polarization, is cleaned by ultrasonic 10min successively with absolute ethyl alcohol, deionized water, dries It is dry;
Chitosan is formulated as aqueous solution, the titanium alloy sample after polarization process is immersed in solution and is sufficiently impregnated, is taken out It air-dries, the above operation of multiplicating 10 times, until being filled up in hole.It can be prepared on medical titanium alloy surface with biological piezoelectricity The composite coating of performance.
Embodiment 3
The Titanium base sample of pretreatment is placed in the stainless steel trough body containing electrolyte, it is stainless using titanium sample as anode Steel tank body is cathode, using pulsed dc voltage, voltage 400V, pulse frequency 500Hz, duty cycle 30%, oxidization time 10min, electrolyte temperature are 60 DEG C.Electrolyte be by solvent be deionized water, solute is the ethylenediamine that concentration is 0.2mol/L The sodium dihydrogen phosphate that calcium acetate that tetraacethyl disodium, concentration are 0.15mol/L, concentration are 0.3mol/L mixes;
The baryta water for accounting for the concentration of reaction kettle total volume 60% as 0.3mol/L is added in into reaction kettle, it will be micro- Titanium sample after arc oxidation processes is positioned in hydrothermal reaction kettle, then at a temperature of 200 DEG C, keeps the temperature 10h;
By above-mentioned steps, treated that sample is polarised in air medium, polarizing voltage 4kV, temperature 60 DEG C, time 2h takes out sample after the completion of polarization, is cleaned by ultrasonic 10min successively with absolute ethyl alcohol, deionized water, drying;
First with absolute ethyl alcohol be cleaned by ultrasonic sample, drying, then by calcium monohydrogen phosphate, anhydrous calcium phosphate, calcium dihydrogen phosphate, One or both of tricalcium phosphate or tetracalcium phosphate nanometer powder are mixed by Ca/P molar ratios for 1.3-2, utilize pressure-air Sample surfaces are sprayed on, the burnishing surface rapid application with one piece of foam that do not absorb water is uniform, with clean and dry softness Superfine fibre cloth gently polishes, and then with absolute ethyl alcohol wipe samples surface once, repeats aforesaid operations 10 times, until in hole With the presence of mixed-powder, vapor is then sprayed on sample surfaces, sprays 5-20min, generates calcium phosphate bone cement.
Embodiment 4
The Titanium base sample of pretreatment is placed in the stainless steel trough body containing electrolyte, it is stainless using titanium sample as anode Steel tank body is cathode, using pulsed dc voltage, voltage 300V, pulse frequency 900Hz, duty cycle 50%, oxidization time 20min, electrolyte temperature are 60 DEG C.Electrolyte be by solvent be deionized water, solute is the ethylenediamine that concentration is 0.5mol/L The sodium dihydrogen phosphate that calcium acetate that tetraacethyl disodium, concentration are 0.5mol/L, concentration are 0.5mol/L mixes;
The baryta water for accounting for the concentration of reaction kettle total volume 65% as 0.1mol/L is added in into reaction kettle, it will be micro- Titanium sample after arc oxidation processes is positioned in hydrothermal reaction kettle, then at a temperature of 220 DEG C, keeps the temperature 16h;
By above-mentioned steps, treated that sample is polarised in air medium, polarizing voltage 5kV, temperature 30 DEG C, time 4h takes out sample after the completion of polarization, is cleaned by ultrasonic 10min successively with absolute ethyl alcohol, deionized water, drying;
It is cleaned by ultrasonic sample with absolute ethyl alcohol first, drying then by nano-Ag particles, is sprayed using pressure-air In sample surfaces, the burnishing surface rapid application with one piece of foam that do not absorb water is uniform, with clean and dry soft superfine fibre Cloth gently polishes, and then with absolute ethyl alcohol wipe samples surface once, repeats aforesaid operations 5 times, until having mixed powder in hole End exists, and vapor then is sprayed on sample surfaces, sprays 15-30min.

Claims (10)

1. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating, which is characterized in that first using differential of the arc oxygen Change technology generates the porous coating of titanium dioxide in inner compact layer, surface layer in titanium alloy substrate surface in situ, then using hydro-thermal Method makes coating of titanium dioxide reaction in-situ generate barium titanate coating, in the hole of the coating surface after finally filling polarization, i.e., The composite coating with biological piezoelectric property is formed on medical titanium alloy surface.
2. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 1, feature It is, the coating of titanium dioxide is rich in Ca, P element.
3. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 1 or 2, special Sign is, specifically implements according to following steps:
Step 1, will be placed in by the titanium alloy substrate sample of pretreatment in the stainless steel trough body containing electrolyte, with titanium alloy-based Body sample is anode, and stainless steel trough body is cathode, using differential arc oxidization technique in titanium alloy substrate specimen surface in-situ preparation The coating of titanium dioxide that layer is fine and close, surface layer is porous;
Step 2, baryta water is added in a kettle, by step 1 differential arc oxidation treated titanium alloy substrate sample It is placed in reaction kettle and carries out hydro-thermal reaction, barium titanate coating is generated in coating of titanium dioxide surface in situ;
Step 3, the titanium alloy substrate sample handled through step 2 is polarised;
Step 4, the hole on the titanium alloy substrate sample coatings surface after wadding warp step 3 polarization process, i.e., in titanium alloy surface Obtain the composite coating with biological piezoelectric property.
4. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, it containing complexing agent concentration is 0.05-0.2mol/L that electrolyte, which is, in the step 1, calcium ion concentration 0.01- 0.5mol/L, phosphorus acid ion concentration be 0.05-0.5mol/L mixed aqueous solution.
5. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 4, feature It is, the complexing agent is citric acid, one kind in disodium ethylene diamine tetraacetate or mixing;Calcium ion source in for calcium acetate, Calcium nitrate, calcium chloride;Phosphate anion is from sodium dihydrogen phosphate, sodium metaaluminate, potassium hydrogen phosphate, potassium dihydrogen phosphate, β-glycerine One or more of sodium phosphate or β-potassium glycerinophosphate.
6. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, differential arc oxidation parameter is in the step 1:Differential arc oxidation uses pulsed dc voltage, voltage 200-500V, pulse frequency Rate is 300-900Hz, and duty cycle 10-50%, electrolyte temperature is less than 60 DEG C, oxidization time 4-20min.
7. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, baryta water concentration is 0.1mol/L-0.3mol/L in the step 2, and addition is reaction kettle total volume 50%-70%;Hydrothermal temperature is 140-220 DEG C, keeps the temperature 6-16h.
8. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, polarized media is any one in air, methyl-silicone oil, transformer oil in the step 3;Polarizing voltage is 1-5kV, Poling temperature is 30-150 DEG C, polarization time 1-5h.
9. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, the material that hole is filled in the step 4 is bioactive substance or anti-microbial type substance.
10. a kind of preparation method of medical titanium alloy surface biological Piezoelectric anisotropy coating according to claim 3, feature It is, fill method is infusion process or nanometer air spray finishing in the step 4.
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