CN101792923A - Method for titanium plate surface nanoscale roughening - Google Patents
Method for titanium plate surface nanoscale roughening Download PDFInfo
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- CN101792923A CN101792923A CN 201010145821 CN201010145821A CN101792923A CN 101792923 A CN101792923 A CN 101792923A CN 201010145821 CN201010145821 CN 201010145821 CN 201010145821 A CN201010145821 A CN 201010145821A CN 101792923 A CN101792923 A CN 101792923A
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Abstract
The invention discloses a method for titanium plate surface nanoscale roughening, which belongs to the technical field of nano materials. In the method, titanium plates are used to prepare titanium dioxide nanotube arrays and then are etched to give the nanoscale roughened surfaced. The surface titanium dioxide nano pore arrays obtained by the method has a pore diameter of about 50 nanometers and a depth to width ratio of 0.5 to 1 and are proved by experiments to be favorable for the growing cells thereon. Compared with the prior art, the method is implemented at normal temperature and pressure, can prepare surface regularly and orderly-arranged nano structures, is simple in process and low in cost and overcomes the drawbacks of non-uniform and irregular material surface nano structures, complex preparation process and high cost of magnetron sputter plating, plasma spraying, surface plastic deformation and the like. The method for performing nano pore modification of the surface of pure titanium plates, researched and developed by the invention, can be industrially produced easily, can obtain large-area nano pore arrays and is expected to be widely used in the field of biomedical materials.
Description
Technical field
What the present invention relates to is a kind of method of technical field of nano material, specifically is that a kind of to prepare the aperture at pure titanium plate surface be about 50 nanometers, and depth-to-width ratio is the method for the titanium plate surface nanoscale roughening of about 1 nanoporous.
Background technology
At biomedical sector, titanium and alloy thereof have obtained using widely because its favorable mechanical performance and biochemical adaptability clinically, and as in plastic surgery, dentistry is implanted, artificial bone, aspects such as skull reparation.
When the organism that carries out material was implanted, direct acting material surface most importantly took place with cell in the influence factor of its effect quality exactly except the mechanical characteristic of material own.In general, the porous surface of roughening more can promote sticking, break up and growing of cell than smooth surface.Implant surface helps absorption of proteins through after the porous alligatoring, thereby can effectively improve the bonding strength of planting body bone interface, and has and promote the effect of bone to differentiation and healing significantly.Therefore, adopting special technique that the titanium material surface is carried out nano level and modify, thereby make it to have more excellent biological compatibility, is the research emphasis that organism is implanted the titanium material surface modifying.
Tradition is used for the titanium material surface is carried out alligatoring, makes nanostructure and has several different methods, comprises alkali heat treating process, magnetron sputtering method, plasma spraying method, surface plastic deformation method etc.But the material surface nanostructure that these methods are prepared is evenly neat inadequately, and complicated process of preparation, expends higher.Anonizing has technology simple as a kind of preparation method of material surface porous-film, advantage with low cost.
Find through retrieval prior art, C.M.Ruan, M.Paulose, O.K.Varghese waits the people at Fabricationof highly ordered TiO
2Nanotube arrays using an organic electrolyte[J] (" adopt organic electrolyte to prepare the TiO of high-sequential
2The method of nano-tube array ") (" Journal of Physical Chemistry " B.2005,109 (33): put down in writing 15754-15759.) in organic electrolyte that to adopt anonizing to prepare pipe range longer, caliber is bigger, and uniform diameter, arrange orderly Nano tube array of titanium dioxide.
Further retrieval is found, Chinese patent literature CN101503211, open day 2009-8-12, put down in writing a kind of " titanium dioxide nano-pore array thin film and preparation method thereof ", this technology adopts porous alumina formwork to prepare titanium dioxide nano-pore array thin film, the nonrepeatability of template and the limitation of complexity of technology its large-scale application; Chinese patent literature CN101307479 open day 20081119, has put down in writing a kind of " TiO
2The preparation method of nanometer pore array material and application thereof ", this technology adopts anonizing to prepare titanium dioxide nano-pore, but its process cycle is long, and the preparation method is comparatively complicated, and the hole homogeneity is not ideal enough.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of method of titanium plate surface nanoscale roughening is provided, adopt anonizing in organic electrolyte, to prepare and arrange uniform sequential Nano tube array of titanium dioxide, adopt the corrosive fluid of specific proportioning that this nano-tube array is corroded afterwards, thereby obtain evenly distributed titanium dioxide nano-pore layer, realized the nanoscale roughening of titanium plate surface is modified.Through the titanium sheet material after this method processing, its biocompatibility is significantly increased.
The present invention is achieved by the following technical solutions, the present invention includes following steps:
Step 1 prepares Nano tube array of titanium dioxide by the titanium sheet: at first prepare organic electrolyte, then the medical titanium sheet is carried out anodic oxidation treatment as anode, platinum electrode as negative electrode, prepare Nano tube array of titanium dioxide;
Described medical titanium sheet is meant that purity is more than or equal to the titanium sheet more than 95%.
Described medical titanium sheet is successively through acetone, dehydrated alcohol and deionized water ultrasonic cleaning 15 minutes and dry.
Described organic electrolyte is meant: by massfraction is that the fluoride salt of 0.3wt%, deionized water and the organic solvent preparation that massfraction is 2wt% obtain;
Described fluoride salt comprises: Neutral ammonium fluoride, Sodium Fluoride or Potassium monofluoride.
Described organic solvent is meant: ethylene glycol or glycerol.
Described anodic oxidation is meant: under 20 ℃ of constant temperatures, the volts DS that applies 20V between anode and the negative electrode carries out oxide treatment.
Step 2, corrosion titanium sheet obtains the nanoscale roughening surface: at first prepare corrosive fluid, the anode after will cleaning then is placed in one and carries out corrosion treatment, realizes titanium plate surface nanoscale roughening through after the aftertreatment.
Described preparation corrosive fluid is meant: adopt concentration to be respectively 25%, 30% ammonia soln and hydrogen peroxide solution and deionized water by 1: 1: 5 mol ratio preparation electrolytic solution;
Anode after the described cleaning is meant: place dehydrated alcohol and deionized water for ultrasonic to clean 5 minutes and drying respectively on anode;
Described corrosion treatment is meant: place 70～80 ℃ corrosive fluid to corrode 20 minutes on anode;
Described aftertreatment is meant: the anode after will corroding takes out, and, is dipped in the deionized water, and changes water once every 1 hour, the triplicate after drying after 5 minutes with the mobile deionized water rinsing.
The aperture of the surface titanium dioxide nanohole array that the present invention prepares is about 50nm, and depth-to-width ratio helps cell through experiment confirm and grows thereon between 0.5 to 1.Compared with prior art the present invention carries out under normal temperature and pressure conditions, and can prepare the surface and arrange regular orderly nanostructure, technology is simple simultaneously, with low cost, overcome magnetron sputtering method, plasma spraying method, the material surface nanostructure that surface plastic deformation method etc. is prepared is evenly neat inadequately, complicated process of preparation expends the higher defective of cost.The present invention developed carries out the method that nanoporous modifies to pure titanium plate surface and is easy to realize industrialization and can obtains large-area nano hole array, will have a wide range of applications in biomedical materials field.
Description of drawings
Fig. 1 is the stereoscan photograph of titania nanotube in the embodiment of the invention;
Among the figure: A is a vertical view, and B is a side-view.
Fig. 2 is the microtexture of titanium dioxide nano-pore in the embodiment of the invention;
Among the figure: A is a stereoscan photograph, and B is the atomic force microscope photo.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Present embodiment may further comprise the steps:
Step 1, substrate preparation.At first,, used acetone, dehydrated alcohol, each ultrasonic cleaning of deionized water (DI water) successively 15 minutes, all use mobile deionized water rinsing and drying for standby each time after the ultrasonic cleaning highly purified medical titanium sheet (95%).
Step 2, preparation organic electrolyte: adopt the Neutral ammonium fluoride of analytical balance weighing 0.335 gram, be dissolved in 2.2 milliliters the deionized water, add 98 milliliters ethylene glycol afterwards, place on the magnetic stirring apparatus and slowly stirred 10 minutes, organic solution is mixed.
Step 3,20 ℃ of constant temperature of system held, as anode, platinum electrode places organic electrolyte as negative electrode with pure titanium sheet, continues to stir after 10 minutes and closes magnetic stirring apparatus.Keep the voltage of 20V, anodic oxidation can make evenly distributed Nano tube array of titanium dioxide at pure titanium plate surface in 2 hours.Its scanning electron microscope image as shown in Figure 1.The titania nanotube that present embodiment makes is arranged uniform sequential, and caliber is about about 50 nanometers, and pipe range is about about 1 micron.
Step 4, the titanium sheet cleans.With grow pure titanium sheet material each ultrasonic cleaning 5 minutes in dehydrated alcohol and deionized water (DI water) successively behind the titania nanotube of anodic oxidation, all use the mobile deionized water rinsing after each ultrasonic cleaning is intact, and drying for standby.
Step 5, the preparation of corrosive fluid: employing concentration is 25% ammoniacal liquor, 30% hydrogen peroxide, and deionized water (DI water) was by 1: 1: 5 mol ratio preparation electrolytic solution.It is 22 milliliters of ammoniacal liquor (0.3 moles) that present embodiment adopts proportioning, 31 milliliters of hydrogen peroxide (0.3 mole), and 27 ml deionized water (1.5 moles).The three is mixed post-heating to 70 ℃ and is incubated 1 to 2 minute.
Step 6, the preparation of titanium dioxide nano-pore.Titanium sheet material after grown titania nanotube and the cleaning is put into corrosive fluid corrosion 20 minutes.The system temperature scope is between 70 ℃ to 80 ℃.
Step 7, the aftertreatment of titanium sheet material.Titanium sheet material after the corrosion is taken out, after 5 minutes, be dipped in the deionized water, and changed water once, take out drying for standby behind the triplicate every 1 hour with the mobile deionized water rinsing.The scanning electronic microscope of the titanium dioxide nano-pore that present embodiment makes and atomic force microscope images as shown in Figure 2, the aperture of nanoporous is about 50 nanometers, depth-to-width ratio is between 0.5 to 1.
Embodiment 2
In the step 2 in the present embodiment, weighing 0.335 gram Sodium Fluoride and 2.2 ml deionized water and 98 milliliters of ethylene glycol are prepared organic electrolyte jointly.In the step 3, under 20 ℃ of constant temperature, adopt 20V voltage anodic oxidation 2 hours.Identical among other steps and the embodiment 1, nano-pore structure that finally makes and embodiment 1 are just the same.
Embodiment 3
In the step 2 in the present embodiment, weighing 0.375 gram Neutral ammonium fluoride and 2.5 ml deionized water and 97 milliliters of glycerol are prepared organic electrolyte jointly.In the step 3, under 20 ℃ of constant temperature, adopt 20V voltage anodic oxidation 10 hours.Identical among other steps and the embodiment 1, nano-pore structure that finally makes and embodiment 1 are just the same.
Claims (10)
1. the method for a titanium plate surface nanoscale roughening is characterized in that, comprises the steps:
Step 1 prepares Nano tube array of titanium dioxide by the titanium sheet: at first prepare organic electrolyte, then the medical titanium sheet is carried out anodic oxidation treatment as anode, platinum electrode as negative electrode, prepare Nano tube array of titanium dioxide;
Step 2, corrosion titanium sheet obtains the nanoscale roughening surface: at first prepare corrosive fluid, the anode after will cleaning then is placed in one and carries out corrosion treatment, realizes titanium plate surface nanoscale roughening through after the aftertreatment.
2. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described medical titanium sheet is successively through acetone, dehydrated alcohol and deionized water ultrasonic cleaning 15 minutes and dry.
3. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described organic electrolyte is meant: by massfraction is that the fluoride salt of 0.3wt%, deionized water and the organic solvent preparation that massfraction is 2wt% obtain.
4. the method for titanium plate surface nanoscale roughening according to claim 3 is characterized in that, described fluoride salt comprises: Neutral ammonium fluoride, Sodium Fluoride or Potassium monofluoride.
5. the method for titanium plate surface nanoscale roughening according to claim 3 is characterized in that, described organic solvent is meant: ethylene glycol or glycerol.
6. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described anodic oxidation is meant: under 20 ℃ of constant temperatures, the volts DS that applies 20V between anode and the negative electrode carries out oxide treatment.
7. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described preparation corrosive fluid is meant: employing concentration is 25% ammoniacal liquor, and 30% hydrogen peroxide solution and deionized water are prepared corrosive fluid by 1: 1: 5 mol ratio.
8. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, the anode after the described cleaning is meant: place dehydrated alcohol and deionized water for ultrasonic to clean 5 minutes and drying respectively on anode.
9. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described corrosion treatment is meant: place 70～80 ℃ corrosive fluid to corrode 20 minutes on anode.
10. the method for titanium plate surface nanoscale roughening according to claim 1 is characterized in that, described aftertreatment is meant: the anode after will corroding takes out, with the mobile deionized water rinsing after 5 minutes, be dipped in the deionized water, and changed water once every 1 hour, the triplicate after drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552977A (en) * | 2012-01-19 | 2012-07-11 | 上海交通大学医学院附属第九人民医院 | Preparation method and application of metal surface-etched nanoporous array |
| CN102776544A (en) * | 2012-07-13 | 2012-11-14 | 西南交通大学 | Preparation technology for semi-wall type titanium dioxide nanotube array |
| CN110253873A (en) * | 2019-04-24 | 2019-09-20 | 常州三提新材料有限公司 | Equipment, method and the film obtained of micro-nano porous structure are generated on film |
| CN111910231A (en) * | 2020-07-22 | 2020-11-10 | 东莞市百镀通五金电镀实业有限公司 | Roughening liquid for roughening glass fiber reinforced plastic and roughening method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307479A (en) * | 2008-01-31 | 2008-11-19 | 上海交通大学 | TiO2 nanometer pore array material preparation method and uses thereof |
| CN101503211A (en) * | 2008-02-04 | 2009-08-12 | 中国科学院合肥物质科学研究院 | Titanium dioxide nano-pore array film and preparation method thereof |
-
2010
- 2010-04-14 CN CN 201010145821 patent/CN101792923A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101307479A (en) * | 2008-01-31 | 2008-11-19 | 上海交通大学 | TiO2 nanometer pore array material preparation method and uses thereof |
| CN101503211A (en) * | 2008-02-04 | 2009-08-12 | 中国科学院合肥物质科学研究院 | Titanium dioxide nano-pore array film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 《上海口腔医学》 20091031 张梅等 钛表面TiO2纳米孔对骨髓基质细胞黏附和铺展的影响 493-498 1-10 第18卷, 第5期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102552977A (en) * | 2012-01-19 | 2012-07-11 | 上海交通大学医学院附属第九人民医院 | Preparation method and application of metal surface-etched nanoporous array |
| CN102776544A (en) * | 2012-07-13 | 2012-11-14 | 西南交通大学 | Preparation technology for semi-wall type titanium dioxide nanotube array |
| CN102776544B (en) * | 2012-07-13 | 2015-06-03 | 西南交通大学 | Preparation technology for semi-wall type titanium dioxide nanotube array |
| CN110253873A (en) * | 2019-04-24 | 2019-09-20 | 常州三提新材料有限公司 | Equipment, method and the film obtained of micro-nano porous structure are generated on film |
| CN110253873B (en) * | 2019-04-24 | 2024-06-04 | 常州三提新材料有限公司 | Apparatus, method for forming micro-nano porous structure on film and film produced thereby |
| CN111910231A (en) * | 2020-07-22 | 2020-11-10 | 东莞市百镀通五金电镀实业有限公司 | Roughening liquid for roughening glass fiber reinforced plastic and roughening method |
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Open date: 20100804 |