CN103110981A - Method for preparing antibacterial active titanium oxide nanotube array composite coating material - Google Patents
Method for preparing antibacterial active titanium oxide nanotube array composite coating material Download PDFInfo
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- CN103110981A CN103110981A CN2013100086239A CN201310008623A CN103110981A CN 103110981 A CN103110981 A CN 103110981A CN 2013100086239 A CN2013100086239 A CN 2013100086239A CN 201310008623 A CN201310008623 A CN 201310008623A CN 103110981 A CN103110981 A CN 103110981A
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Abstract
The invention discloses a method for preparing an antibacterial active titanium oxide nanotube array composite coating material. The method comprises the following steps of: performing electrolytic oxidation to prepare a titanium oxide nanotube array with biological activity by taking titanium and an alloy thereof as an anode, taking an electrolyte solution containing phosphate anion and fluorinion as electrolyte; soaking the titanium oxide nanotube array with biological activity in the solution of silver nitrate and polyethylene glycol which are taken as a soaking solution, taking the titanium oxide nanotube array out, inducing the light in the active titanium oxide nanotube array to deposit silver particles through UV-irradiation, and obtaining the titanium oxide nanotube array composite coating material with the antibacterial property and biological activity. According to the material prepared by the method, the silver particles enter the titanium alloy or a titanium alloy matrix, and the material has long-term antibacterial stability; the thickness of the active titanium oxide nanotube array can be controlled in a range from 100 to 1000nm, and bone cell growth and nutrition transfer are promoted; the active titanium oxide generated through anodic oxidation can prevent release of titanium ion in the matrix, and the corrosion resistance of the matrix is improved; and moreover, the coating material has obvious biological activity and can induce bone apatite formation.
Description
Technical field
The present invention relates to a kind of preparation method with anti-microbial property and bioactive composite coating material, belong to the bone reparing biological material technology of preparing.
Background technology
Titanium or titanium alloy has good biocompatibility and mechanical property, is widely used in the bone reparation.Titanium or titanium alloy belongs to bio-inert material, and biological activity is relatively poor, and without antibiotic property.After its implant into body, the heteroplasmon as the host exists all the time, easily deforms, becomes flexible, and causes implant to lose efficacy.After utilizing process for modifying surface to give its biological activity, can make new bone Direct precipitation form synostosis in titanium alloy surface, avoid forming the fiber sheath, make it form chemical combination with host tissue.Have bioactive surface and often also provide for adhering to of antibacterial the hotbed that grows.Dentary graft materials for example, because transplant is exposed in this complicated microbial environment of oral cavity, wound surface place between transplant and body easily is inflamed, and inflammation has become except the factors such as operation technique technology, biomechanics, patient's self-condition on every side, the major reason that causes implantation body's storage rate to descend.Therefore guaranteeing that titanium alloy surface has the bioactive while, will guarantee that also it has the key issue that antibiotic property is present titanium bone grafting material research.
In recent years, construct at titanium alloy surface the focus that research that activity has a bioactive titania nanotube array composite coating is just becoming current research by anodizing technology.(Biomaterials, 26 (2005) 4938) such as Oh S.H. have reported the titania nanotube array with the NaOH treatment titanium alloy surface, have prepared to have bioactive titania nanotube array.Xiao Xiufeng etc. (Materials Science-Poland, 27(2009) 23-31) prepared the composite coating material of hydroxyapatite embedding titania nanotube array.Xiao Xiufeng etc. (CN200810070648.0) have invented a kind of by regulating the anodic oxidation electrolyte composition, utilize one step of anodizing to prepare the bone renovating material with bioactive titania nanotube array coating.
Although these methods have effectively activated titanium alloy surface, make it have biological activity, because it does not also have anti-microbial property, for clinical practice, the risk that the inflammation around embedded material occurs still exists, and has limited its application clinically.
Summary of the invention
The objective of the invention is to be to provide a kind of preparation method that namely has a kind of antibiotic, the active oxidation titanium nano-tube array composite coating material of titanium hypergene thing coating that biological activity has again antibiotic property.
The invention is characterized in: as anode, as electrolyte, electrolytic oxidation is prepared has bioactive titania nanotube array with the electrolyte solution of phosphorus-containing acid ion and fluorion with titanium and alloy thereof; With silver nitrate and Polyethylene Glycol as soak; To have after bioactive titania nanotube array is soaked in silver nitrate and polyglycol solution, taking-up is induced at active oxidation titanium nano-tube array interior lights depositing silver particle by ultraviolet lighting, obtains having antibiotic property and bioactive titania nanotube array coating material.Specifically comprise the following steps:
1) preparation of active oxidation titanium nano-tube array: as anode, graphite flake or platinized platinum are containing the Na of 5-10g/L as negative electrode with titanium or titanium alloy ti6al4v matrix
2HPO
40.5wt%HF solution in, with the voltage anodic oxidation of 10-30V 20-40 minutes, take out, clean with distilled water, after the room temperature oven dry, be placed in the temperature control chamber type electric resistance furnace, with 300-500 ℃ of insulations 1-4 hours.
2) AgNO
3The preparation of soak: take successively Polyethylene Glycol, potassium nitrate and silver nitrate and be dissolved in distilled water, preparation becomes and contains AgNO
30.05-0.1 molL
-1, contain Polyethylene Glycol 5.9-11.8 gL
-1, contain potassium nitrate 5-10gL
-1Mixed solution, namely get AgNO
3Soak.
3) soak: the titanium or the titanium alloy that the surface for preparing in step 1 are had active oxidation titanium nano-tube array are soaked in the AgNO3 soak, and soaking temperature is 16-25 ℃, and soak time is 2-6 minutes.
4) UV light-induced: the titanium with active oxidation titanium nano-tube array or the titanium alloy that have soaked the AgNO3 soak in step 3 are placed under the 365nm uviol lamp, and the control intensity of light source is 1400mwcm
-2, continue the radiation-induced of 2-6 minutes.Then use distilled water ultrasonic cleaning sample, and 100 ℃ of oven dry.
Advantage of the present invention and beneficial effect are:
The matrix titanium, titanium oxide nanotubes and the silver-colored doped and compounded coating material that adopt such scheme to obtain have following features:
1. to go deep into titanium alloy or titanium alloy substrate inner for silver particles, avoided it to break away from matrix free out, has long-term antibacterial stability.
2. active oxidation titanium nano-tube array thinner thickness, can be controlled in the 100nm-1000nm scope, hot strength, fracture toughness on matrix can not produce the essence impact, and the porous feature on surface can reduce the difference of implant and flexible bone modulus, be conducive to the growth of osteocyte and the transmission of nutrition, integrate thereby obtain the physiology bone.
3. the active oxidation titanium of anodic oxidation generation can stop the release of titanium ion in matrix, improves the corrosion resistance of matrix.
4. have obvious biological activity, can induce osteolith to form.
Description of drawings:
Fig. 1 is the material surface microstructure picture for preparing by method of the present invention under scanning electron microscope;
Fig. 2 is by the material surface energy spectrogram of method preparation of the present invention.
Fig. 3 be material by method of the present invention preparation after bacterium culture test, the picture of obvious inhibition zone appears around material;
Fig. 4 is that under scanning electron microscope, the material by method of the present invention preparation soaks the surface topography picture that 7 days rear surfaces have osteolith to form in soaking simulated body fluid.
The specific embodiment:
Embodiment 1
A kind of preparation of antibiotic, active oxidation titanium nano-tube array composite coating material, concrete steps are as follows:
(1), the preparation of active oxidation titanium nano-tube array: take pure titanium as matrix, the surface after abrasive paper for metallograph polishing, cleaning, oven dry as anode, take the spectroscopically pure graphite sheet as negative electrode, to contain 5g/LNa
2HPO
40.5wt%HF solution be electrolyte, taking out after anodic oxidation 20min under 20V voltage, dry after at 500 ℃ of insulations 1 hour, furnace cooling;
(2), AgNO
3The preparation of soak: once take Polyethylene Glycol, potassium nitrate and silver nitrate and be dissolved in distilled water, preparation becomes and contains AgNO
30.1 molL
-1, contain Polyethylene Glycol 11.8 gL
-1, contain potassium nitrate 10gL
-1Mixed solution;
(3), soak: immersion contains AgNO under 25 ℃
30.1 molL
-1, contain Polyethylene Glycol 11.8 gL
-1, contain potassium nitrate 10gL
-1Mixed solution in soaked 6 minutes.
(4), UV light-induced: as will to have soaked AgNO in step 3
3The titanium with active oxidation titanium nano-tube array of soak takes out and to carry out UV Light and induce, and is placed under the 365nm uviol lamp, and the control intensity of light source is 1400mwcm
-2, after UV Light is induced 6min, with distilled water ultrasonic cleaning sample, namely get antibiotic, active oxidation titanium nano-tube array composite coating after 100 ℃ of oven dry.
With the material surface pattern of this method preparation as shown in Figure 1, the part mouth of pipe is faintly visible, and the part mouth of pipe covers thin layer, and surface microscopic figure illustrates that this material surface is even, porous; Through the energy dispersive spectrometry analysis, as shown in Figure 2, no matter be that mouth of pipe visibility region or the mouth of pipe cover coating region, result shows the Ag content that 1-3wt% is all arranged, and proves that silver successfully adulterates.
Embodiment 2:
A kind of preparation of antibiotic, active oxidation titanium nano-tube array composite coating material, concrete steps are as follows:
(1), the preparation of active oxidation titanium nano-tube array: take titanium alloy ti6al4v as matrix, the surface after abrasive paper for metallograph polishing, cleaning, oven dry as anode, take the spectroscopically pure graphite sheet as negative electrode, to contain 10g/LNa
2HPO
40.5wt%HF solution be electrolyte, taking out after anodic oxidation 40min under 20V voltage, dry after at 500 ℃ of insulations 2 hours, furnace cooling.
(2), AgNO
3The preparation of soak: once take Polyethylene Glycol, potassium nitrate and silver nitrate and be dissolved in distilled water, preparation becomes and contains AgNO30.1 molL
-1, contain Polyethylene Glycol 5.9 gL
-1, contain potassium nitrate 5gL
-1Mixed solution;
(3), soak: immersion contains AgNO under 20 ℃
30.1 molL
-1, contain Polyethylene Glycol 5.9 gL
-1, contain potassium nitrate 5gL
-1Mixed solution 4 minutes.
(4), UV light-induced: as will to have soaked AgNO in step 3
3The taking-up of the titanium alloy with active oxidation titanium nano-tube array of soak is carried out UV Light and is induced, and is placed under the 365nm uviol lamp, and the control intensity of light source is 1400mwcm
-2, after UV Light is induced 4min, with distilled water ultrasonic cleaning sample, namely get antibiotic, active oxidation titanium nano-tube array composite coating after 100 ℃ of oven dry.
Utilize the material of method preparation of the present invention, have obvious anti-microbial property, the effectively breeding of anti-bacteria, material obvious inhibition zone occurs around material, as shown in Figure 3 after bacterium culture test.
Utilize the material of method preparation of the present invention, have obvious biological activity, can induce osteolith to form, material soaks 7 days rear surfaces in soaking simulated body fluid have osteolith to form, as shown in Figure 4.
Claims (1)
1. the preparation of antibiotic, an active oxidation titanium nano-tube array composite coating material is characterized in that:
1) preparation of active oxidation titanium nano-tube array: as anode, graphite flake or platinized platinum are containing the Na of 5-10g/L as negative electrode with titanium or titanium alloy ti6al4v matrix
2HPO
40.5wt%HF solution in, with the voltage anodic oxidation of 10-30V 20-40 minutes, take out, clean with distilled water, after the room temperature oven dry, be placed in the temperature control chamber type electric resistance furnace, with 300-500 ℃ of insulations 1-4 hours;
2) AgNO
3The preparation of soak: take successively Polyethylene Glycol, potassium nitrate and silver nitrate and be dissolved in distilled water, preparation becomes and contains AgNO
30.05-0.1 molL
-1, contain Polyethylene Glycol 5.9-11.8 gL
-1, contain potassium nitrate 5-10gL
-1Mixed solution, namely get AgNO
3Soak;
3) soak: the titanium or the titanium alloy that the surface for preparing in step 1 are had active oxidation titanium nano-tube array are soaked in AgNO
3Soak, soaking temperature is 16-25 ℃, soak time is 2-6 minutes;
4) UV light-induced: as will to have soaked AgNO in step 3
3Titanium with active oxidation titanium nano-tube array or the titanium alloy of soak are placed under the 365nm uviol lamp, and the control intensity of light source is 1400mwcm
-2, continue the radiation-induced of 2-6 minutes; Then use distilled water ultrasonic cleaning sample, and 100 ℃ of oven dry.
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| CN103526259A (en) * | 2013-10-08 | 2014-01-22 | 广州中国科学院先进技术研究所 | Titanium alloy operation apparatus surface treatment technology |
| CN103628112A (en) * | 2013-11-20 | 2014-03-12 | 内蒙金属材料研究所 | Preparation method of titanium-base titanium oxide-silver chloride composite coating material |
| CN103695707A (en) * | 2013-10-18 | 2014-04-02 | 中国医科大学 | Titanium silver alloy nanotube for surgery fixing apparatus and preparation method thereof |
| CN103768663A (en) * | 2014-01-07 | 2014-05-07 | 东南大学 | Long-acting antibacterial absorbable bone surgical appliance material and preparation method thereof |
| CN104131325A (en) * | 2014-07-18 | 2014-11-05 | 中国兵器工业第五二研究所 | Preparation method of titanium oxide nano-tube array-silver composite coating material |
| CN105506711A (en) * | 2016-01-25 | 2016-04-20 | 东北农业大学 | Method for preparing double-side TiO2 nanotube array material with surface modified by silver nanoparticles through ultrasonic atomization-ultraviolet reduction combination |
| CN106752113A (en) * | 2016-12-14 | 2017-05-31 | 浙江恒逸高新材料有限公司 | A kind of preparation method of modifying titanium dioxide and application |
| CN107096068A (en) * | 2017-03-15 | 2017-08-29 | 北京科技大学 | A kind of preparation method of dentistry implant and its bioactivity antimicrobial surface |
| CN108744047A (en) * | 2018-06-11 | 2018-11-06 | 浙江理工大学 | A kind of preparation method of titanium nanometer/fibroin albumen/hydroxyapatite composite medical titanium coating |
| CN108926741A (en) * | 2018-06-20 | 2018-12-04 | 复旦大学附属华山医院 | A kind of preparation method of amnion biological sticking patch |
| CN109289089A (en) * | 2018-10-15 | 2019-02-01 | 福建师范大学 | The preparation method of temperature control intelligent medicine releasing system based on Nano tube array of titanium dioxide |
| CN110621356A (en) * | 2017-03-21 | 2019-12-27 | 国际商业机器公司 | Antimicrobial medical implant surfaces |
| CN111569146A (en) * | 2020-05-12 | 2020-08-25 | 淮阴工学院 | Preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility |
| CN112545713A (en) * | 2020-11-23 | 2021-03-26 | 天衍医疗器材有限公司 | Bone filling prosthesis and preparation process thereof |
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| CN103526259B (en) * | 2013-10-08 | 2016-08-17 | 广州市健齿生物科技有限公司 | A kind of titanium alloy operating theater instruments process of surface treatment |
| CN103526259A (en) * | 2013-10-08 | 2014-01-22 | 广州中国科学院先进技术研究所 | Titanium alloy operation apparatus surface treatment technology |
| CN103695707A (en) * | 2013-10-18 | 2014-04-02 | 中国医科大学 | Titanium silver alloy nanotube for surgery fixing apparatus and preparation method thereof |
| CN103628112A (en) * | 2013-11-20 | 2014-03-12 | 内蒙金属材料研究所 | Preparation method of titanium-base titanium oxide-silver chloride composite coating material |
| CN103628112B (en) * | 2013-11-20 | 2015-10-28 | 内蒙金属材料研究所 | A kind of preparation method of titanium based titanium oxide silver chloride composite coating material |
| CN103768663A (en) * | 2014-01-07 | 2014-05-07 | 东南大学 | Long-acting antibacterial absorbable bone surgical appliance material and preparation method thereof |
| CN103768663B (en) * | 2014-01-07 | 2015-01-21 | 东南大学 | Long-acting antibacterial absorbable bone surgical appliance material and preparation method thereof |
| CN104131325A (en) * | 2014-07-18 | 2014-11-05 | 中国兵器工业第五二研究所 | Preparation method of titanium oxide nano-tube array-silver composite coating material |
| CN105506711A (en) * | 2016-01-25 | 2016-04-20 | 东北农业大学 | Method for preparing double-side TiO2 nanotube array material with surface modified by silver nanoparticles through ultrasonic atomization-ultraviolet reduction combination |
| CN106752113B (en) * | 2016-12-14 | 2019-02-19 | 浙江恒逸高新材料有限公司 | A kind of preparation method and application of modifying titanium dioxide |
| CN106752113A (en) * | 2016-12-14 | 2017-05-31 | 浙江恒逸高新材料有限公司 | A kind of preparation method of modifying titanium dioxide and application |
| CN107096068A (en) * | 2017-03-15 | 2017-08-29 | 北京科技大学 | A kind of preparation method of dentistry implant and its bioactivity antimicrobial surface |
| CN110621356A (en) * | 2017-03-21 | 2019-12-27 | 国际商业机器公司 | Antimicrobial medical implant surfaces |
| CN110621356B (en) * | 2017-03-21 | 2022-07-15 | 国际商业机器公司 | Antimicrobial medical implant surfaces |
| CN108744047A (en) * | 2018-06-11 | 2018-11-06 | 浙江理工大学 | A kind of preparation method of titanium nanometer/fibroin albumen/hydroxyapatite composite medical titanium coating |
| CN108744047B (en) * | 2018-06-11 | 2021-08-13 | 浙江理工大学 | Preparation method of titanium nano/silk fibroin/hydroxyapatite composite medical titanium coating |
| CN108926741A (en) * | 2018-06-20 | 2018-12-04 | 复旦大学附属华山医院 | A kind of preparation method of amnion biological sticking patch |
| CN108926741B (en) * | 2018-06-20 | 2021-05-25 | 复旦大学附属华山医院 | Preparation method of amnion biological patch |
| CN109289089A (en) * | 2018-10-15 | 2019-02-01 | 福建师范大学 | The preparation method of temperature control intelligent medicine releasing system based on Nano tube array of titanium dioxide |
| CN109289089B (en) * | 2018-10-15 | 2021-12-28 | 福建师范大学 | Preparation method of temperature-controlled intelligent drug release system based on titanium dioxide nanotube array |
| CN111569146A (en) * | 2020-05-12 | 2020-08-25 | 淮阴工学院 | Preparation method of medical titanium material loaded with Sr and Ag and capable of improving biocompatibility |
| CN112545713A (en) * | 2020-11-23 | 2021-03-26 | 天衍医疗器材有限公司 | Bone filling prosthesis and preparation process thereof |
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