CN101565824A - Ultraviolet light irradiation method for increasing surface biological activity of titanium or alloy thereof - Google Patents
Ultraviolet light irradiation method for increasing surface biological activity of titanium or alloy thereof Download PDFInfo
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- CN101565824A CN101565824A CNA2009101412154A CN200910141215A CN101565824A CN 101565824 A CN101565824 A CN 101565824A CN A2009101412154 A CNA2009101412154 A CN A2009101412154A CN 200910141215 A CN200910141215 A CN 200910141215A CN 101565824 A CN101565824 A CN 101565824A
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Abstract
The invention relates to a method for modifying surface of medical metal material, especially to an ultraviolet light irradiation method for increasing surface biological activity of titanium or alloy thereof. The method includes steps of oxidizing titanium and alloy thereof at low temperature by using mixed solution of hydrogen peroxide and hydrochloric acid, and carrying out ultraviolet light irradiation; wherein the oxidizing temperature is 50-100DEG C, and the oxidizing time is 0.5-8 hours. The invention can increases surface biological activity and strength of the titanium and alloy thereof, has no special requirement to shape and size of sample, can form uniform biological activity film formation without crack so as to be especially suitable for basal body with complicated shape, and can be widely used for replacing hard tissue such as joint, tooth, bone and skull bone of human body. The invention has simple process, lower energy consumption and cost relative to plasma spraying, and simple operation, and is easy to popularization.
Description
Technical field
The present invention relates to method in the medical metal material surface modification, be meant that specifically a kind of UV-irradiation improves titanium and the bioactive method of alloy surface thereof, the method that belongs to titanium and alloy surface modifying thereof, titanium and alloy thereof after the modification are specially adapted to neurocranial surgery.
Background technology
Pure titanium and alloy thereof because of its good biocompatibility, mechanical property, erosion resistance and preferably processability be widely used in the replacement of the sclerous tissues such as joint, tooth, bone of human body, but because titanium and alloy thereof all are inert materials, the ubiquity biological activity is poor behind the implant into body,, healing time low with the growth synosteosis intensity problem of waiting so long.The titanium dioxide film on titanium surface is the passivation layer of one deck densification, though certain biocompatibility is arranged, almost there is not biological activity, induce the ability extreme difference of phosphatoptosis, even can not induce, the reaction between human body and titanium and the alloy thereof mainly is the reaction between this layer oxidation titanium film and the human body.Titanium and alloy surface oxide film thereof are carried out modification, make its surperficial biologically active, can with the bone forming chemical bonding, and can substitute the focus that function of organization becomes this type of research at present for a long time.
TiO
2Having a kind of special photoresponse phenomenon is exactly photocatalytic phenomenon.TiO
2Under the irradiation of UV-light, the valence band electronics can be energized into conduction band, and produces electron-hole pair, and this electron-hole pair has stronger redox ability, a lot of organic pollutants in the oxidable air.Simultaneously, under UV-irradiation, form more activity hydroxy group on the surface of titanium and alloy thereof, the contact angle of simulated body fluid and surface of metal titanium is reduced greatly, in simulated body fluid, this helps the formation and the growth of osteoid apatite.
Chinese patent 200510023170.2 discloses a kind of method for preparing the nano-titanium oxide coating layer of biologically active.Because nano-titanium oxide has excellent biological compatibility, under UV-irradiation, the surface forms a large amount of activity hydroxy groups, is immersed in the simulated body fluid, and osteoid apatite forms on the surface.What this patent of invention adopted is the plasma spraying nano-titanium oxide, and coating and matrix bond are better, do not have obvious crack, but the plasma spraying energy consumption is bigger, and is difficult to obtain uniform coating on complex-shaped matrix.
Chinese patent 200610015425.5 discloses a kind of method of oxidation film on titanium alloy surface by ultraviolet excitation fast growing HA biologically active rete.Thermal treatment can obtain the oxide film on surface, but pyroprocessing easily makes film surface crack, and itself and high base strength are reduced.
Summary of the invention
The object of the invention is to overcome above-mentioned the deficiencies in the prior art part, provides a kind of and can not only significantly improve the material biological activity, can also make the UV-irradiation of the corresponding raising of its intensity improve titanium and the bioactive method of alloy surface thereof.
Above-mentioned purpose of the present invention reaches by following measure.
A kind of UV-irradiation improves titanium and the bioactive method of alloy surface thereof, and it is characterized in that: carry out UV-irradiation on the basis of cryochemistry oxidation, its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
It is (1) titanium and alloy polishing thereof is extremely smooth,
(2) use acetone, dehydrated alcohol, deionized water supersound washing to clean successively,
(3) hydrogen peroxide and hydrochloric acid mixed solution titanium oxide and alloy thereof, oxidizing temperature is 50~100 ℃, oxidization time is 0.5~8h;
Step 2: UV-irradiation
(1) preparation of simulated body fluid: according to the prescription of Kukubo T, with chemical reagent in accordance with regulations order add in the deionized water, under 37 ℃, pH value and ionic concn are adjusted to consistent with human body fluid,
(2) UV-irradiation: earlier with titanium after the oxidation and alloy cleaning-drying thereof, be immersed in then and carry out UV-irradiation in the simulated body fluid, its ultraviolet light intensity is 400~700W, and the distance between titanium and alloy thereof and the light source is 30~40cm, and irradiation time is 20min~2h;
Step 3: mineralising
Titanium after the oxidation illumination and alloy thereof are put into simulated body fluid, and mineralising is 1~7 day in 37 ℃ of constant temperature shaking tables, simulated body fluid of replacing at least 2 days.
Described hydrogen peroxide of step 1 (3) and hydrochloric acid mixed solution are meant the mixing solutions of 30% hydrogen peroxide and 36% hydrochloric acid, and its volume ratio is 1~3: 1.
The described pH value of step 2 (1) is to regulate pH value to 7.40 with basic solution.
The prescription of described step 2 (1) simulated body fluid is NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4
Each ionic concentration is in the above-mentioned simulated body fluid: Na
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L.
The suitable strength of described UV-light is 700w, and the optimum distance between titanium and alloy thereof and the light source is 30cm, and best irradiation time is 2h.
The present invention compared with prior art has following outstanding advantage:
1, the present invention adopts the method that the cryochemistry oxidation combines with UV-irradiation, and intensity also has corresponding raising when titanium and alloy surface biological activity thereof significantly improve.Owing to adopt the method for cryochemistry oxidation, to compare with the thermal oxidative treatment surface, the oxide film of generation is because of without pyroprocessing, and there is not crackle in the gained rete; Because UV-irradiation is given surface titanium dioxide activity hydroxy group, improved surperficial wetting ability effectively, and made its biologically active again; Shortened the time that in simulated body fluid, generates HA.
2, because the present invention does not have particular requirement to the material shape size, all can form uniform bioactive film, therefore be specially adapted to complex-shaped matrix, treated titanium and alloy thereof can be widely used in the replacement of sclerous tissueses such as the joint, tooth, bone of human body, comprise the cranium brain bone that difficulty is bigger.
3, technology of the present invention is simple, and with respect to plasma spraying, energy consumption is lower and easy and simple to handle, and cost is lower, is easy to promote.
4, the simulated body fluid that adopts of the present invention equates with corresponding ionic concn in the human body fluid, and material mineralization ability therein is the biological activity behind the reaction material implant into body preferably.
Embodiment
Embodiment 1
It is to carry out UV-irradiation on the basis of cryochemistry oxidation that a kind of UV-irradiation improves the bioactive method of surface of metal titanium, and its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
With 10 * 10 * 1mm
3Titanium sheet (Ti) uses 180#, 280#, 360#, 600#, 800#, 1000# sand papering to smooth successively, use 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively, washing is to clean back hydrogen peroxide and hydrochloric acid mixed solution oxidation, oxidizing temperature is 100 ℃, and oxidization time is 8h; The required mixing solutions 40ml of oxidising process, adopting 30% hydrogen peroxide and 36% hydrochloric acid also is preparation in 3: 1 by volume.
Step 2: UV-irradiation
The preparation of simulated body fluid: according to the prescription of Kukubo T, with a certain amount of NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4Join successively in the deionized water, under 37 ℃, use the pH value to 7.40 of the NaOH regulator solution of 1mol/L, each ionic concn is respectively Na in the simulated body fluid that makes thus
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L; Under 37 ℃, regulate pH value to 7.40 with basic solution, reach consistent with the concentration of human body fluid same ion.
UV-irradiation: earlier with the titanium sheet cleaning-drying after the oxidation, be immersed in then and carry out UV-irradiation in the simulated body fluid, its ultraviolet light intensity is 700W, and the distance between titanium sheet and the light source is 30cm, and irradiation time is 2h.
Step 3: mineralising
Titanium sheet after the oxidation illumination is put into the 50ml neoallotype intend body fluid, divided other mineralising 1 day, 3 days at 37 ℃ of constant temperature shaking table chats (2 days change one time simulated body fluid).The titanium plate surface adularescent rete of mineralising after 1 day generates, and mineralising is after 3 days, and white film is covered with the surface, illustrates that its biological membranous layer prolongs in time and thickens, and biological activity also can be better relatively.
Titanium sheet before and after the UV-irradiation is carried out the contact angle test, the static contact angle of titanium sheet obviously reduces after the UV-irradiation, embodiment 1 gained material mineralising is carried out the contact angle test after 3 days, be reduced to 18.1 ° for preceding 25.6 ° by UV-irradiation, illustrates to have biological activity preferably.
Embodiment 2
It is to carry out UV-irradiation on the basis of cryochemistry oxidation that a kind of UV-irradiation improves the bioactive method of surface of metal titanium, and its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
Use 180#, 280#, 360#, 600#, 800#, 1000# sand papering to smooth successively Φ 4 * 10mm titanium rod (Ti), use 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively, washing is to clean back hydrogen peroxide and hydrochloric acid mixed solution oxidation, oxidizing temperature is 85 ℃, and oxidization time is 5h; The required mixing solutions 40ml of oxidising process, adopting 30% hydrogen peroxide and 36% hydrochloric acid also is preparation in 2: 1 by volume.
Step 2: UV-irradiation
The preparation of simulated body fluid: according to the prescription of Kukubo T, with a certain amount of NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4Join successively in the deionized water, under 37 ℃, use the pH value to 7.40 of the NaOH regulator solution of 1mol/L, each ionic concn is respectively Na in the simulated body fluid that makes thus
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L; Under 37 ℃, regulate pH value to 7.40 with basic solution, reach consistent with the concentration of human body fluid same ion.
UV-irradiation: with the rod of the titanium after oxidation cleaning-drying, be immersed in then and carry out UV-irradiation in the simulated body fluid earlier, its ultraviolet light intensity is 500W, and the distance between titanium rod and the light source is 35cm, and irradiation time is 1h.
Step 3: mineralising
Titanium rod after the oxidation illumination is put into the simulated body fluid that 50ml newly joins, and mineralising is 3 days in 37 ℃ of constant temperature shaking tables, changes simulated body fluid one time in 2 days, and the titanium rod surface after the mineralising generates the rete of one deck white.
Titanium rod before and after the UV-irradiation is carried out the contact angle test, and the static contact angle of titanium rod obviously reduces after the UV-irradiation, is reduced to 19.2 ° for preceding 25.2 ° by UV-irradiation, illustrates to have biological activity preferably.
Embodiment 3
It is to carry out UV-irradiation on the basis of cryochemistry oxidation that a kind of UV-irradiation improves the bioactive method of titanium alloy surface, and its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
Use 180#, 280#, 360#, 600#, 800#, 1000# sand papering to smooth successively Φ 4 * 10mm titanium alloy rod (Ti6Al4V), use 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively, washing is to clean back hydrogen peroxide and hydrochloric acid mixed solution oxidation, oxidizing temperature is 50 ℃, and oxidization time is 8h; The required mixing solutions 20ml of oxidising process, adopting 30% hydrogen peroxide and 36% hydrochloric acid also is preparation in 1: 1 by volume.
Step 2: UV-irradiation
The preparation of simulated body fluid: according to the prescription of Kukubo T, with a certain amount of NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4Join successively in the deionized water, under 37 ℃, use the pH value to 7.40 of the NaOH regulator solution of 1mol/L, each ionic concn is respectively Na in the simulated body fluid that makes thus
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L under 37 ℃, regulates pH value to 7.40 with basic solution, reaches consistent with the concentration of human body fluid same ion;
UV-irradiation: with the rod of the titanium alloy after oxidation cleaning-drying, be immersed in then and carry out UV-irradiation in the simulated body fluid earlier, its ultraviolet light intensity is 400W, and the distance between titanium alloy rod and the light source is 40cm, and irradiation time is 20min;
Step 3: mineralising
Titanium alloy rod after the oxidation illumination is put into the simulated body fluid that 50ml newly joins, and mineralising is 7 days in 37 ℃ of constant temperature shaking tables, changes simulated body fluid one time in per 2 days, and the titanium alloy rod surface after the mineralising generates the rete of one deck white.
Titanium alloy rod before and after the UV-irradiation is carried out the contact angle test, and the static contact angle of titanium alloy rod obviously reduces after the UV-irradiation, is reduced to 19.5 ° for preceding 30.2 ° by UV-irradiation, illustrates that its biological activity is better.
Embodiment 4
It is to carry out UV-irradiation on the basis of cryochemistry oxidation that a kind of UV-irradiation improves the bioactive method of titanium net surface, and its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
With 10 * 10 * 1mm
3Titanium net (Ti) uses 180#, 280#, 360#, 600#, 800#, 1000# sand papering to smooth successively, use 99.5% acetone, 99.7% dehydrated alcohol, each ultrasonic cleaning 20min of deionized water then successively, washing is to clean back hydrogen peroxide and hydrochloric acid mixed solution oxidation, oxidizing temperature is 75 ℃, and oxidization time is 3h; The required mixing solutions 35ml of oxidising process, adopting 30% hydrogen peroxide and 36% hydrochloric acid also is preparation in 2.5: 1 by volume.
Step 2: UV-irradiation
The preparation of simulated body fluid: according to the prescription of Kukubo T, with a certain amount of NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4Join successively in the deionized water, under 37 ℃, use the pH value to 7.40 of the NaOH regulator solution of 1mol/L, each ionic concn is respectively Na in the simulated body fluid that makes thus
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1,0mmol/L, SO
4 2-=0.5mmol/L under 37 ℃, regulates pH value to 7.40 with basic solution, reaches consistent with the concentration of human body fluid same ion,
UV-irradiation: earlier with the titanium net cleaning-drying after the oxidation, be immersed in then and carry out UV-irradiation in the simulated body fluid, its ultraviolet light intensity is 600W, and the distance between titanium net and the light source is 30cm, and irradiation time is 1.5h;
Step 3: mineralising
Titanium net after the oxidation illumination is put into the simulated body fluid that 50ml newly joins, and mineralising is 2 days in 37 ℃ of constant temperature shaking tables, and the titanium net surface of mineralising after 2 days generates the rete of one deck white.
Titanium net before and after the UV-irradiation is carried out the contact angle test, and the static contact angle of titanium net obviously reduces after the UV-irradiation, is reduced to 18.6 ° for preceding 27.6 ° by UV-irradiation, illustrates that its biological activity is better.
Claims (6)
1, a kind of UV-irradiation improves titanium and the bioactive method of alloy surface thereof, and it is characterized in that: carry out UV-irradiation on the basis of cryochemistry oxidation, its method may further comprise the steps and processing condition:
Step 1: cryochemistry oxidation
It is (1) titanium and alloy polishing thereof is extremely smooth,
(2) use acetone, dehydrated alcohol, deionized water supersound washing to clean successively,
(3) hydrogen peroxide and hydrochloric acid mixed solution titanium oxide and alloy thereof, oxidizing temperature is 50~100 ℃, oxidization time is 0.5~8h;
Step 2: UV-irradiation
(1) preparation of simulated body fluid: according to the prescription of Kukubo T, with chemical reagent in accordance with regulations order add in the deionized water, under 37 ℃, pH value and ionic concn are adjusted to consistent with human body fluid,
(2) UV-irradiation: earlier with titanium after the oxidation and alloy cleaning-drying thereof, be immersed in then and carry out UV-irradiation in the simulated body fluid, its ultraviolet light intensity is 400~700W, and the distance between titanium and alloy thereof and the light source is 30~40cm, and irradiation time is 20min~2h;
Step 3: mineralising
Titanium after the oxidation illumination and alloy thereof are put into simulated body fluid, and mineralising is 1~7 day in 37 ℃ of constant temperature shaking tables, simulated body fluid of replacing at least 2 days.
2, a kind of UV-irradiation according to claim 1 improves titanium and the bioactive method of alloy surface thereof, it is characterized in that: described hydrogen peroxide of step 1 (3) and hydrochloric acid mixed solution are meant the mixing solutions of 30% hydrogen peroxide and 36% hydrochloric acid, and its volume ratio is 1~3: 1.
3, a kind of UV-irradiation according to claim 1 improves titanium and the bioactive method of alloy surface thereof, it is characterized in that: the described pH value of step 2 (1) is to regulate pH value to 7.40 with basic solution.
4, a kind of UV-irradiation according to claim 1 improves titanium and the bioactive method of alloy surface thereof, and it is characterized in that: the prescription of described step 2 (1) simulated body fluid is NaCl, NaHCO
3, Na
2CO
3, KCl, K
2HPO
43H
2O, N-(2-hydroxyethyl)-piperazidine N '-(4-butane sulfonic acid), MgCl
26H
2O, CaCl
2, Na
2SO
4
5, a kind of UV-irradiation according to claim 4 improves titanium and the bioactive method of alloy surface thereof, and it is characterized in that: each ionic concentration is in the described simulated body fluid: Na
+=142.0mmol/L, K
+=5.0mmol/L, Mg
2+=1.5mmol/L, Ca
2+=2.5mmol/L, Cl
-=103.0mmol/L, HCO
3 -=27.0mmol/L, HPO
4 2-=1.0mmol/L, SO
4 2-=0.5mmol/L.
6, a kind of UV-irradiation according to claim 1 improves titanium and the bioactive method of alloy surface thereof, and it is characterized in that: described ultraviolet light intensity is 700w, and the distance between titanium and alloy thereof and the light source is 30cm, and irradiation time is 2h.
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CN106880870A (en) * | 2017-03-07 | 2017-06-23 | 珠海乔丹科技股份有限公司 | A kind of processing method of titanium-based implant surface activation |
CN106958014A (en) * | 2017-04-06 | 2017-07-18 | 西南交通大学 | The method for building organic inorganic hybridization function and service coating in pure magnesium surface |
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2009
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CN101880874A (en) * | 2010-07-12 | 2010-11-10 | 西安交通大学 | Method for improving surface hydrophilicity of medical titanium or titanium alloy |
CN101880874B (en) * | 2010-07-12 | 2011-11-16 | 西安交通大学 | Method for improving surface hydrophilicity of medical titanium or titanium alloy |
CN106880870A (en) * | 2017-03-07 | 2017-06-23 | 珠海乔丹科技股份有限公司 | A kind of processing method of titanium-based implant surface activation |
CN106958014A (en) * | 2017-04-06 | 2017-07-18 | 西南交通大学 | The method for building organic inorganic hybridization function and service coating in pure magnesium surface |
CN106958014B (en) * | 2017-04-06 | 2019-05-17 | 西南交通大学 | In the method for pure magnesium surface building hybrid inorganic-organic function and service coating |
CN113262331A (en) * | 2021-05-26 | 2021-08-17 | 成都百瑞恒通医疗科技有限公司 | Dense mesh stent for promoting endothelialization and preparation method thereof |
CN113797398A (en) * | 2021-09-26 | 2021-12-17 | 苏州纽创医疗科技有限公司 | Preparation method of titanium alloy stent with anticoagulant coating and stent |
CN114272436A (en) * | 2021-12-28 | 2022-04-05 | 陈栋 | Surface chemical modification method for dental implant combined with alveolar bone and application |
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Open date: 20091028 |