CN100467669C - Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation - Google Patents
Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation Download PDFInfo
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- CN100467669C CN100467669C CNB2006100154255A CN200610015425A CN100467669C CN 100467669 C CN100467669 C CN 100467669C CN B2006100154255 A CNB2006100154255 A CN B2006100154255A CN 200610015425 A CN200610015425 A CN 200610015425A CN 100467669 C CN100467669 C CN 100467669C
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Abstract
the invention discloses an oxide-film rapid growing method of HA biological active layer on the ultraviolet laser Ti-alloy surface, which comprises the following steps: (1) oxidizing through heat; (2) irradiating through ultraviolet; (3) allocating soaking liquid of analog; (4) immersing to grow HA coating layer through analogy soaking liquid.
Description
(1) technical field:
The invention belongs in medical metal and the bionical preparation bioactive layer of alloy surface technology, particularly relate to a kind of ultraviolet excitation titanium alloy surface heat oxide film, and then the method for hydroxyapatite (HA) bioactive layer of in simulated body fluid (SBF), growing fast.
(2) background technology:
At present, titanium alloy is carried out the biological activity surface treatment, the method for preparing hydroxyapatite (HA) coating is a lot, and technology commonly used comprises: plasma spraying, laser melting coating, sol-gel, electrochemical deposition, micro-arc oxidation, bionical solution growth, ion beam assisted depositing etc.Wherein bionical solution growth method not only has the advantages such as processing that cost is low, easy and simple to handle, bonding strength is high and be applicable to various complex devices, also simulate the forming process of inanimate matter in the natural bone especially, had very strong researching value and broad clinical application prospect.
The gordian technique of bionical solution growth method is that acid, alkalization learn to be handled, and direct relation that titanium alloy surface is active to be had or not and strong and weak.Adopt this method in the laboratory, to carry out small sample at present and handle problems such as still the existence surface is inhomogeneous, technology is unstable, need pre-calcification, and preparation cycle is long, limited this technology applying in commercially producing.In order to give full play to the advantage that bionical solution growth method prepares biological activity HA coating process, shorten the preparation cycle of coating, reduce power consumption, reach the purpose that environmental protection is produced, develop a kind of new activating process replacing acid, alkalization is learned and handled is necessary.
So far, have the investigator to handle at titanium and alloy surface thereof by high-temperature thermal oxidation and form titanium dioxide film, manage corrosive while improving abrasion resistance and antibiosis, it is immersed in the simulated body fluid also can induce the HA deposition by the electrostatic attraction effect, but its cycle is longer, needs 7 ~ 14 days approximately.Report that monocrystalline or polycrystal titanium dioxide produce Superhydrophilic through making the surface after the UV-irradiation, promptly UV-light can excite titanium dioxide surface hydroxyl radical free radical (OH), superoxide ion (O
2 -) formation of isoreactivity group.Therefore, after the UV-light width of cloth is according to the titanium alloy surface after handling through high-temperature thermal oxidation, the active group that forms reduces the infiltration angle of simulated body fluid and titanium alloy surface greatly, thereby significantly reduces the heterogeneous nucleation merit of hydroxyapatite alloy surface, promotes the quick growth of HA.This by ultraviolet excitation titanium alloy surface heat oxide film, the method for biomimetic growth HA coating still is not reported both at home and abroad in simulated body fluid.
(3) summary of the invention:
The objective of the invention is to design a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer, it improves the hydrophilic process for treating surface of titanium dioxide surface with titanium alloy surface thermooxidizing and ultraviolet light irradiation and combines, be used for coating at simulated body fluid biomimetic growth HA, in the bionic components and excellent biological compatibility that keep coating, activating process replacing acid with oxidation and ultraviolet light irradiation, alkalization is learned and is handled, simplify technological process, lower power consumption, environmental protection is also shortened the preparation cycle of coating, make the bionical HA preparation technology of coating of titanium alloy surface be more suitable for commercially producing, thereby satisfy clinically to human loaded bone, hard tissue repair alternate demands such as tooth are benefited the damaged patient of millions upon millions of bones.
Technical scheme of the present invention: a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer is characterized in that it may further comprise the steps:
(1) thermal oxidative treatment: the titanium alloy sample is after polishing, carry out ultrasonic cleaning, drying respectively, carry out thermal oxidative treatment then under 400 ~ 800 ℃ of temperature, oxidization time is 2-6h, obtains anatase octahedrite and the rutile suitable titanium deoxid film of ratio mutually with this;
(2) ultraviolet light irradiation: with the irradiation under the UV-light of varying strength of the sample after the oxidation, sample has the distance that is not less than 10cm apart from radiation source, and the intensity of light source is 100-500W, irradiation time 1-5h, and the wetting ability of sample before and after the illumination tested;
(3) preparation simulated body fluid soak solution: the prescription of simulated body fluid soak solution is that certain amount of neutral and meta-alkalescence chemical reagent and sustained release dosage are dissolved in the deionized water, under human body normal temperature, with the pH value of acidic solution regulator solution to 7.4-7.5, reach with human body fluid in the concentration of same ion suitable;
(4) soak with simulated body fluid: be removed the sample after the oxidation illumination is soaked 1d-5d respectively in simulated body fluid after, the clean surface residue is also dry.
Thermal oxidative treatment atmosphere in the above-mentioned said step (1) is atmosphere or oxygen.
The prescription of simulated body fluid soak solution is NaCl and KCl and Na in the above-mentioned said step (3)
2HPO
412H
2O and Na
2CO
3And MgCl
26H
2O and CaCl
2(CH
2OH)
3CNH
2
Each ionic concn is respectively in the simulated body fluid of preparing in the above-mentioned said step (3): Na
+=142.0mmol/L, Cl
-=125.0mmol/L, HCO
3 -=27.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L.
Principle of work of the present invention is: the invention reside in provides a kind of ultraviolet excitation titanium alloy surface heat oxide film, increases wetting ability, promotes the method for biomimetic growth HA coating in simulated body fluid.This method is by changing the oxidizing temperature and the time of titanium alloy surface, the crystalline structure of regulation and control alloy table oxide compound, and the time and intensity of control UV-irradiation, make the surface produce Superhydrophilic, be immersed in the simulated body fluid,, make quick forming core of HA and growth by electrostatic forcing.
Superiority of the present invention is: 1, the method that adopts titanium alloy surface thermooxidizing and ultraviolet light irradiation to combine, and by ultraviolet excitation TiO
2The valence band electronic migration, produce electron-hole pair at alloy surface, form great amount of hydroxy group free radical (OH) active group, not only improve the wetting ability of titanium alloy surface effectively, but also make its biologically active, be easier to biomimetic growth HA coating in simulated body fluid; 2, adopting the used time of this poling processing technique is 3-5h, only be in the past acid-alkali treatment and pre-calcification activating process required time about 1/10; 3, because ultraviolet lighting has improved the wetting property of alloy surface to simulated body fluid effectively, the cycle of HA layer growth also by original 3-5 days, is kept to 1 day, has simplified schedule of operation thus greatly, has shortened the treatment time, has increased efficient, has reduced energy consumption; 4, avoided strong acid, highly basic to handle in this technological process, environmental protection is pollution-free, and it is unrestricted to the size of processing apparatus, complex-shaped degree, and can form uniform bioactive layer, for medical metal and alloy surface bioactive coating technology of preparing really are applied to the clinical valid approach of having opened up.
(4) description of drawings:
The titanium alloy surface HA coating structure synoptic diagram of accompanying drawing 1 for forming in the method for the related oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer of the present invention.
Wherein:
1 is titanium alloy, comprises Ti, Ti6Al4V, TiAlNb, TiNbSn, TiMoZrSn, TiAlFe etc.;
2 is titanium dioxide transition layer (Anatase/Rutile), be the preparation of thermal oxidative treatment under different oxidizing temperatures, the titanium dioxide film densification of more spontaneous formation, even through having Superhydrophilic after the UV photoinduction, is rich in the Ti-OH group that brings out the phosphatic rock forming core;
3 is hydroxyapatite (HA), and biomimetic growth forms in the simulated body fluid in order to be immersed in after thermal oxidative treatment and UV photoinduction.
(5) embodiment:
Embodiment 1: a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer is characterized in that it may further comprise the steps:
(1) thermal oxidative treatment: with the Ti-Nb-Sn alloy sample of 10 * 10 * 1mm after the abrasive paper for metallograph polishing, carry out ultrasonic cleaning, drying respectively with acetone and deionized water, in resistance furnace, carry out thermal oxidative treatment then, oxidizing temperature is respectively 500 ℃, 600 ℃ and 700 ℃, oxidization time 3h, oxidizing atmosphere is atmosphere, obtains anatase octahedrite and the rutile suitable titanium deoxid film of ratio mutually with this, determines best oxidizing process parameter;
(2) ultraviolet light irradiation: with the irradiation under the UV-light of varying strength of the sample after the oxidation, sample is 20mm apart from the distance of radiation source, intensity of light source 150W and 300W, irradiation time is 2h, adopt quiet contact angle measurement that the wetting ability of sample before and after the illumination is tested, determine best illumination processing parameter;
(3) preparation simulated body fluid soak solution: with a certain amount of NaCl, KCl, Na
2HPO12H
2O, Na
2CO
3, MgCl
26H
2O, CaCl
2, (CH
2OH)
3CNH
2Be dissolved in the deionized water Deng chemical reagent, at 37 ℃, with the pH value to 7.4 of 1N hydrochloric acid conditioning solution, each ionic concn is respectively in Pei Zhi the simulated body fluid thus: Na
+=142.0mmol/L, Cl
-=125.0mmol/L, HCO
3 -=27.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L is suitable with the concentration of same ion in the human body fluid;
(4) simulated body fluid soaks: be removed the sample after the oxidation illumination is soaked 1d-5d respectively in simulated body fluid after, the washed with de-ionized water surface residue is also dry.
Embodiment 2: a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer is characterized in that it may further comprise the steps:
(1) thermal oxidative treatment: with the Ti-6Al-4V alloy sample of 10 * 10 * 1mm after the abrasive paper for metallograph polishing, carry out ultrasonic cleaning, drying respectively with acetone and deionized water, in the controlled atmosphere resistance furnace, carry out thermal oxidative treatment then, oxidizing temperature is respectively 300 ℃, 400 ℃ and 500 ℃, oxidization time 1h, oxidizing atmosphere is oxygen, obtains anatase octahedrite and the rutile suitable titanium deoxid film of ratio mutually with this, determines best oxidizing process parameter;
(2) ultraviolet light irradiation: with the irradiation under the UV-light of varying strength of the sample after the oxidation, sample is 20mm apart from the distance of radiation source, the intensity of light source 100 and 500W, irradiation time 1h, adopt quiet contact angle measurement that the wetting ability of sample before and after the illumination is tested, determine best illumination processing parameter;
(3) preparation simulated body fluid soak solution: with a certain amount of NaCl, KCl, Na
2HPO12H
2O, Na
2CO
3, MgCl
26H
2O, CaCl
2, (CH
2OH)
3CNH
2Be dissolved in the deionized water Deng chemical reagent, at 37 ℃, with the pH value to 7.4 of 1N hydrochloric acid conditioning solution, each ionic concn is respectively in Pei Zhi the simulated body fluid thus: Na
+=142.0mmol/L, Cl
-=125.0mmol/L, HCO
3 -=27.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L is suitable with the concentration of same ion in the human body fluid;
(4) simulated body fluid soaks: be removed the sample after the oxidation illumination is soaked 1d-5d respectively in simulated body fluid after, the washed with de-ionized water surface residue is also dry.
Claims (4)
1, a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer is characterized in that it may further comprise the steps:
(1) thermal oxidative treatment: the titanium alloy sample is after polishing, carry out ultrasonic cleaning, drying respectively, carry out thermal oxidative treatment then under 400 ~ 800 ℃ of temperature, oxidization time is 2-6h, obtains anatase octahedrite and the rutile suitable titanium deoxid film of ratio mutually with this;
(2) ultraviolet light irradiation: with the irradiation under the UV-light of varying strength of the sample after the oxidation, sample has the distance that is not less than 10cm apart from radiation source, and the intensity of light source is 100-500W, irradiation time 1-5h, and the wetting ability of sample before and after the illumination tested;
(3) preparation simulated body fluid soak solution: the prescription of simulated body fluid soak solution is that certain amount of neutral and meta-alkalescence chemical reagent and sustained release dosage are dissolved in the deionized water, under human body normal temperature, with the pH value of acidic solution regulator solution to 7.4-7.5, reach with human body fluid in the concentration of same ion suitable;
(4) soak with simulated body fluid: be removed the sample after the oxidation illumination is soaked 1d-5d respectively in simulated body fluid after, the clean surface residue is also dry.
2,, it is characterized in that the thermal oxidative treatment atmosphere in the said step (1) is atmosphere or oxygen according to the method for the said a kind of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer of claim 1.
3,, it is characterized in that the prescription of simulated body fluid soak solution in the said step (3) is NaCl and KCl and Na according to the method for the said a kind of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer of claim 1
2HPO
412H
2O and Na
2CO
3And MgCl
26H
2O and CaCl
2(CH
2OH)
3CNH
2
4, according to the method for the said a kind of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active layer of claim 1, each ionic concn is respectively in the simulated body fluid that it is characterized in that preparing in the said step (3): Na
+=142.0mmol/L, Cl
-=125.0mmol/L, HCO
3 -=27.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L.
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|---|---|---|---|
| CNB2006100154255A CN100467669C (en) | 2006-08-23 | 2006-08-23 | Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation |
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| CNB2006100154255A CN100467669C (en) | 2006-08-23 | 2006-08-23 | Method of fast growing HA biologically active layer from oxidation film on titanium alloy surface by ultraviolet excitation |
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| CN100467669C true CN100467669C (en) | 2009-03-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051569B (en) * | 2011-01-26 | 2012-12-19 | 沈阳工业大学 | Method for preparing titanium/hydroxyapatite composite coating |
| CN113082290B (en) * | 2019-12-23 | 2022-09-16 | 北京科技大学天津学院 | Zinc oxide coating-hydroxyapatite coating with bioactivity and antibacterial performance, preparation method and application |
| CN115976468A (en) * | 2022-12-22 | 2023-04-18 | 深圳怡诚新材料有限公司 | Super-hydrophilic film layer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6033780A (en) * | 1995-07-07 | 2000-03-07 | Maruo Calcium Company Limited | Fine particles of petaloid porous hydroxyapatite and process for producing the same |
| CN1417378A (en) * | 2002-12-02 | 2003-05-14 | 天津大学 | Chemical process of preparing bioactive hydroxy apatite layer on the surface of NiTi alloy |
| CN1546178A (en) * | 2003-12-17 | 2004-11-17 | 西北有色金属研究院 | Technique for coating porous titanium surface with hydroxyapatite layer |
| CN1712076A (en) * | 2004-06-15 | 2005-12-28 | 中国科学院金属研究所 | Surface treatment for improving bioactivity and wear-resistant ability of titanium alloy surfaces |
-
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- 2006-08-23 CN CNB2006100154255A patent/CN100467669C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6033780A (en) * | 1995-07-07 | 2000-03-07 | Maruo Calcium Company Limited | Fine particles of petaloid porous hydroxyapatite and process for producing the same |
| CN1417378A (en) * | 2002-12-02 | 2003-05-14 | 天津大学 | Chemical process of preparing bioactive hydroxy apatite layer on the surface of NiTi alloy |
| CN1546178A (en) * | 2003-12-17 | 2004-11-17 | 西北有色金属研究院 | Technique for coating porous titanium surface with hydroxyapatite layer |
| CN1712076A (en) * | 2004-06-15 | 2005-12-28 | 中国科学院金属研究所 | Surface treatment for improving bioactivity and wear-resistant ability of titanium alloy surfaces |
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