CN103451705A - Preparation method of gold-loaded nanotube thin film on surface of medical titanium - Google Patents
Preparation method of gold-loaded nanotube thin film on surface of medical titanium Download PDFInfo
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- CN103451705A CN103451705A CN2013103431936A CN201310343193A CN103451705A CN 103451705 A CN103451705 A CN 103451705A CN 2013103431936 A CN2013103431936 A CN 2013103431936A CN 201310343193 A CN201310343193 A CN 201310343193A CN 103451705 A CN103451705 A CN 103451705A
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Abstract
The invention relates to a preparation method of a gold-loaded nanotube thin film on the surface of medical titanium. The preparation method comprises the following steps: carrying out in-situ oxidation on the surface of medical titanium through constant voltage direct current anodic oxidation so as to generate a regular titanium oxide nanotube array thin film; adsorbing and loading chloroauric acid in titanium oxide nanotubes; soaking the titanium oxide nanotube array thin film in a solution which has the pH value of 7.0-8.0 and contains a chloroauric acid solution, standing still for 2 to 8 hours at the constant temperature of 37 DEG C, taking out, cleaning, and drying for 1 to 4 hours at the temperature of 50-80 DEG C so as to obtain the titanium oxide nanotube array thin film on which the chloroauric acid is adsorbed and loaded; and carrying out thermal treatment on the titanium oxide nanotube array thin film on which the chloroauric acid is adsorbed and loaded for 2 to 6 hours at 100-650 DEG C, thus obtaining the gold-loaded titanium oxide nanotube array thin film.
Description
Technical field
The present invention relates to a kind of medical titanium surface and carry the preparation method of gold nanotubes film, be specifically related to a kind of employing constant voltage DC anodizing technique and generate the titanium oxide nanotubes film in the oxidation of medical titanium surface in situ, then take the wet-chemical mode that nm gold particles is loaded in titanium oxide nanotubes, thereby obtain the method for carrying the gold nanotubes film on the medical titanium surface, belong to nano material preparation and metal surface properties modification technical field.
Background technology
The biologically inert of bio-medical metal implant, the weak grade of being combined with osseous tissue is the subject matter of its clinical effectiveness of restriction always.After the not good major embodiment of its bone integration ability is the implant into body tissue, the osteogenesis albumen such as the Fibronectin in internal milieu can not effectively adhere at implant surfaces, affect follow-up skeletonization relevant cell adhering to and sprawling on its surface, and then affect propagation and the differentiation of cell, the newly-generated osseous tissue of final impact can not with the effective combination of implant, cause implant inefficacy (Biomaterials2004,25 (19): 4731-4739.).
It is to promote its biological activity, the effective way of bone integration ability that biomedical metallic material is carried out to surface modification.Constant voltage DC anodizing technology can be at the titanium oxide nanotubes film of medical titanium material surface in situ oxidation create-rule, research finds that the nanotube pattern can significantly promote osteoblastic adhering to, propagation and functional expression (Nano Letters2007,7 (6): 1686-1691.).In addition, nm gold particles is because of its hypotoxicity, and good spectral response and stablize the advantages such as bonding with Protein formation is widely used in biological diagnosis and treatment field (Chemical Society Reviews2012,41 (7): 2740-2779.).Therefore, if add carried nano-gold in titanium oxide nanotubes, can promote in conjunction with both advantages the bone integration ability of medical titanium material.About carrying the preparation method of golden titanium oxide nanotubes, for example adopt electrodip process at present, for example the disclosed mixed deposit liquid ultrasonic electric deposition preparation Au/TiO that Nano tube array of titanium dioxide is placed in to hydrochloro-auric acid and boric acid in Chinese patent 102863046A
2nano-tube array, disclosed in Chinese patent CN101320010B Nano tube array of titanium dioxide is placed in to the sulfuric acid containing hydrochloro-auric acid, the Ag/AgCl of take obtains the titanium dioxide electrodes of decorated by nano-gold by potentiostatic electrodeposition as reference electrode, but these methods possibly can't make nanometer gold be carried on titania nanotube uniformly and stably.Again for example in Chinese patent CN102360958B the open mixing solutions that Nano tube array of titanium dioxide is placed in to sodium hydroxide solution and chlorauric acid solution by the hydro-thermal sedimentation directly in 130～150 ℃ carry out hydro-thermal reaction by Au nanoparticle uniform deposition at the nanotube inside and outside wall, but the pattern of nanotube rule is affected.
Summary of the invention
The present invention is for the biologically inert that solves the medical titanium material existed in prior art and the bone integration ability is not good etc. that a difficult problem is made, its purpose is to provide a kind of medical titanium surface to carry the preparation method of gold nanotubes film, can be in the situation that guarantee the titania nanotube array complete shape and appearance, efficiently and easily in nanotube, load nm gold particles, effective tubular looks of combining nano and the nm gold particles bone integration ability that is used for promoting the medical titanium material to cell and albumen, to fill up the blank of prior art.
At this, the invention provides the preparation method that the gold nanotubes film is carried on a kind of medical titanium surface, described method comprises:
(1) titania nanotube array film at medical titanium surface in situ oxidation create-rule by the constant voltage DC anodizing;
(2) hydrochloro-auric acid is loaded in titanium oxide nanotubes absorption: described titania nanotube array film is soaked in the solution that the pH containing hydrochloro-auric acid solution is 7.0～8.0, standing 2～8 hours of 37 ℃ of constant temperature, take out after cleaning and within 1～4 hour, obtain in 50 ℃～80 ℃ drying and processings the titania nanotube array film that hydrochloro-auric acid is loaded in absorption; And
(3) titania nanotube array film that hydrochloro-auric acid is loaded in absorption, in 100～650 ℃ of thermal treatments 2～6 hours, obtains carrying golden titania nanotube array film.
Year gold nanotubes film prepared through technique of the present invention, retain the nano-tube array surface topography, and nm gold particles is uniformly distributed in nano-tube film simultaneously, is embedded in nanotube walls, in conjunction with good.Carry the gold nanotubes film and embody good albumen affinity, thereby improve biological activity and the bone integration ability of medical titanium material.
Preferably, in described step (1), the negative electrode of described constant voltage DC anodizing can be Graphite Electrodes or platinum electrode, and electrolytic solution can be the mass percent hydrofluoric acid solution that is 0.1～1.0%, anodic oxidation voltage can be 5～30V, and oxidization time can be 0.5～2 hour.
Preferably, in described step (2), dropwise add sodium hydroxide solution that concentration is 0.1～1mol/L in the chlorauric acid solution that the solution that the described pH containing hydrochloro-auric acid solution is 7.0～8.0 can be is 0.1～10mmol/L in concentration until the pH value is 7.0～8.0 obtained.
Preferably, in described step (3), can be to be warming up to 100～650 ℃ with 1～5 ℃/min.
The accompanying drawing explanation
Fig. 1 (a) is scanning electron microscope (SEM) picture that surface of metal titanium is not carried golden titania nanotube array film;
Fig. 1 (b) carries scanning electron microscope (SEM) picture of golden titania nanotube array film for surface of metal titanium;
Fig. 2 is that transmission electron microscope (TEM) picture in gold nanotubes film cross section is carried on the medical titanium surface;
Fig. 3 is energy dispersion X ray (EDS) spectrogram that the gold nanotubes film is carried on the medical titanium surface;
Fig. 4 is x-ray photoelectron (XPS) power spectrum that the gold nanotubes film is carried on the medical titanium surface.
Embodiment
Further illustrate the present invention below in conjunction with accompanying drawing and following embodiment, should be understood that following embodiment is only for the present invention is described, and unrestricted the present invention.
The present invention is for the biologically inert that solves the medical titanium material existed in prior art and the difficult problem such as the bone integration ability is not good, provide a kind of medical titanium surface to carry the preparation method of gold nanotubes film, can be in the situation that guarantee the titania nanotube array complete shape and appearance, efficiently and easily in nanotube, load nm gold particles, effective tubular looks of combining nano and the nm gold particles bone integration ability that is used for promoting the medical titanium material to cell and albumen, to fill up the blank of prior art.
As example, the present invention can comprise the following steps.
At first, use constant voltage DC anodizing technique to prepare regular titanium oxide nanotubes film in the oxidation of medical titanium surface in situ.
While using constant voltage DC anodizing technique, medical titanium is anode, and Graphite Electrodes or platinum electrode are negative electrode.Electrolytic solution is the hydrofluoric acid solution that mass percent is 0.1～1.0%, and anodic oxidation voltage is 5～30V, and oxidization time is 0.5～2 hour.In a preferred example embodiment, it is the hydrofluoric acid solution that mass percent is 1.0% that the processing parameter of constant voltage DC anodizing can be electrolytic solution, and anodic oxidation voltage can be 20V, and oxidization time can be 0.5 hour.
Then, use wet chemical method to load nm gold particles in the regular titanium oxide nanotubes film of medical titanium surface preparation.
Use chlorauric acid solution, concentration is 0.1～10mmol/L.Then dropwise add the sodium hydroxide solution regulator solution pH value to 7.0 that concentration is 0.1-1mol/L～8.0.In a preferred example embodiment, can in the chlorauric acid solution of 1mmol/L, dropwise add the sodium hydroxide solution of 1mol/L.In another preferred example embodiment, can regulator solution pH value to 7.2.
Get chlorauric acid solution and soak titanium oxide nanotubes.The volume of chlorauric acid solution is not limit, as long as can complete submergence titanium oxide nanotubes.Then put into 37 ℃ of constant incubators standing 2～8 hours.In a preferred example embodiment, it can be standing 4 hours.Then take out sample, rinse gently with ultrapure water, then put into 50 ℃～80 ℃ baking ovens, process in air atmosphere 1～4 hour.In another preferred example embodiment, can be to put into 70 ℃ of baking ovens, in air atmosphere, process 2 hours.
Sample through oven carries out 100～650 ℃ of thermal treatments, so that the hydrochloro-auric acid thermolysis that absorption is loaded obtains nm gold particles.Temperature rise rate is 1～5 ℃/min, is incubated 2～6 hours, furnace cooling.In a preferred example embodiment, can be to carry out 300 ℃ of thermal treatments, temperature rise rate is 1 ℃/min, is incubated 2 hours, furnace cooling.
Year gold nanotubes film made through technique of the present invention, retain the nano-tube array surface topography, and nm gold particles is uniformly distributed in nano-tube film simultaneously, is embedded in nanotube walls, in conjunction with good.Carry the gold nanotubes film and embody good albumen affinity, thereby improve biological activity and the bone integration ability of medical titanium material.
Below further for example embodiment to describe the present invention in detail.Should understand equally; following examples only are used to further illustrate the present invention; and can not be interpreted as limiting the scope of the invention, some nonessential improvement that those skilled in the art's foregoing according to the present invention is made and adjustment all belong to protection scope of the present invention., those skilled in the art can do in suitable scope by the explanation of this paper and select, and not really want to be defined in the hereinafter concrete numerical value of example the temperature of reaction that following example is concrete, time, concentration etc. are only also examples in OK range.
Embodiment 1
(1) by the medical titanium material after polished finish, use successively acetone, alcohol and the ultrasonic cleaning of deionized water water 30 minutes, obtain clean surface uniformly;
(2) preparation anodic oxidation electrolyte: deionized water is solvent, the HF acid electrolyte that dose volume per-cent is 1.0%;
(3) adopt constant voltage DC anodizing technology, at medical titanium material surface in situ oxidation create-rule titania nanotube array film, processing parameter is: medical titanium is anode, and Graphite Electrodes or platinum plate electrode are negative electrode, anodic oxidation voltage is 20V, and oxidization time is 0.5 hour;
(4), after prepared by medical titanium rule of surface titania nanotube array film, clean successively 5 minutes seasoning with dehydrated alcohol and deionized water;
(5) preparation chlorauric acid solution: deionized water is solvent, and compound concentration is the 1mmol/L chlorauric acid solution, and dropwise adds the 1mol/L sodium hydroxide solution, regulator solution pH value to 7.2;
(6) get in the 1ml chlorauric acid solution and soak titanium oxide nanotubes, then put into 37 ℃ of constant incubators standing 4 hours; Then take out sample, rinse gently with ultrapure water, then put into 70 ℃ of baking ovens, process 2 hours in air atmosphere;
(7) sample through oven carries out 300 ℃ of thermal treatments, and temperature rise rate is 1 ℃/min, is incubated 2 hours, and furnace cooling can obtain of the present invention year gold nanotubes film.
Fig. 1 (a) is scanning electron microscope (SEM) picture that surface of metal titanium is not carried golden titania nanotube array film, Fig. 1 (b) carries scanning electron microscope (SEM) picture of golden titania nanotube array film for surface of metal titanium, comparison diagram 1(a) do not carry the surface microscopic topographic of golden titanium oxide nanotubes in, can see that wet chemical method processing rear oxidation titanium nanotube surfaces externally and internally has nm gold particles to adhere to from Fig. 1 (b).Fig. 2 is that the transmission electron microscope picture in gold nanotubes film cross section is carried on the medical titanium surface, can find out that nm gold particles is evenly distributed on nanotube surface and inside.Fig. 3 is the energy dispersion X ray spectrum that the gold nanotubes film is carried on the medical titanium surface, and X-coordinate is x-ray photon energy (KeV), and ordinate zou is the x-ray photon counting, and the film surface composition contains Ti as can be seen from Figure, O and Au.Fig. 4 is the x-ray photoelectron power spectrum (XPS) that the gold nanotubes film is carried on the medical titanium surface, X-coordinate is that orbital electron is in conjunction with energy (KeV), ordinate zou is the photoelectron number detected in the unit time, the figure illustrates the position that the Au4f spectrum peak is positioned at 84.2eV and 87.8eV, these two combinations can be combined and can match with the 4f7/2 of simple substance Au and the orbital electron of 4f5/2, have illustrated that what be combined in that medical titanium nano surface pipe film loads is the metal simple-substance gold.
Embodiment 2
(1) by the medical titanium material after polished finish, use successively acetone, alcohol and the ultrasonic cleaning of deionized water water 30 minutes, obtain clean surface uniformly;
(2) preparation anodic oxidation electrolyte: deionized water is solvent, the HF acid electrolyte that dose volume per-cent is 1.0%;
(3) adopt constant voltage DC anodizing technology, at medical titanium material surface in situ oxidation create-rule titania nanotube array film, processing parameter is: medical titanium is anode, and Graphite Electrodes or platinum plate electrode are negative electrode, anodic oxidation voltage is 20V, and oxidization time is 0.5 hour;
(4), after prepared by medical titanium rule of surface titania nanotube array film, clean successively 5 minutes seasoning with dehydrated alcohol and deionized water;
(5) preparation chlorauric acid solution: deionized water is solvent, and compound concentration is the 1mmol/L chlorauric acid solution, and dropwise adds the 1mol/L sodium hydroxide solution, regulator solution pH value to 7.0;
(6) get in the 1ml chlorauric acid solution and soak titanium oxide nanotubes, then put into 37 ℃ of constant incubators standing 6 hours; Then take out sample, rinse gently with ultrapure water, then put into 70 ℃ of baking ovens, process 2 hours in air atmosphere;
(7) sample through oven carries out 500 ℃ of thermal treatments, and temperature rise rate is 1 ℃/min, is incubated 2 hours, and furnace cooling can obtain of the present invention year gold nanotubes film.
Embodiment 3
(1) by the medical titanium material after polished finish, use successively acetone, alcohol and the ultrasonic cleaning of deionized water water 30 minutes, obtain clean surface uniformly;
(2) preparation anodic oxidation electrolyte: deionized water is solvent, the HF acid electrolyte that dose volume per-cent is 1.0%;
(3) adopt constant voltage DC anodizing technology, at medical titanium material surface in situ oxidation create-rule titania nanotube array film, processing parameter is: medical titanium is anode, and Graphite Electrodes or platinum electrode are negative electrode, anodic oxidation voltage is 20V, and oxidization time is 0.5 hour;
(4), after prepared by medical titanium rule of surface titania nanotube array film, clean successively 5 minutes seasoning with dehydrated alcohol and deionized water;
(5) preparation chlorauric acid solution: deionized water is solvent, and compound concentration is the 1mmol/L chlorauric acid solution, and dropwise adds the 1mol/L sodium hydroxide solution, regulator solution pH value to 8.0;
(6) adopt wet chemical method to load nm gold particles, get in the 1ml chlorauric acid solution and soak titanium oxide nanotubes, then put into 37 ℃ of constant incubators standing 4 hours; Then take out sample, rinse gently with ultrapure water, then put into 70 ℃ of baking ovens, process 4 hours in air atmosphere;
(7) sample through oven carries out 100 ℃ of thermal treatments, and temperature rise rate is 1 ℃/min, is incubated 2 hours, and furnace cooling can obtain of the present invention year gold nanotubes film.
Industrial applicability: within of the present invention year, the gold nanotubes film embodies good albumen affinity ability, this affinity ability is expected to strengthen the absorption of medical titanium material to albumen, accelerate the adhesion of cell on its surface, active cell is bred fast, differentiation waits physiology cascade activity, accelerate osteogenesis, can be applicable to the fields such as bio-medical metal implant.
Claims (4)
1. the preparation method of a medical titanium surface year gold nanotubes film, is characterized in that, comprising:
(1) titania nanotube array film at medical titanium surface in situ oxidation create-rule by the constant voltage DC anodizing;
(2) hydrochloro-auric acid is loaded in titanium oxide nanotubes absorption: described titania nanotube array film is soaked in the solution that the pH containing hydrochloro-auric acid solution is 7.0～8.0, standing 2～8 hours of 37 ℃ of constant temperature, take out after cleaning and within 1～4 hour, obtain in 50～80 ℃ of drying and processings the titania nanotube array film that hydrochloro-auric acid is loaded in absorption; And
(3) titania nanotube array film that hydrochloro-auric acid is loaded in absorption, in 100～650 ℃ of thermal treatments 2～6 hours, obtains carrying golden titania nanotube array film.
2. preparation method according to claim 1, it is characterized in that, the negative electrode of described constant voltage DC anodizing is Graphite Electrodes or platinum electrode, and electrolytic solution is the hydrofluoric acid solution that mass percent is 0.1～1.0%, anodic oxidation voltage is 5～30V, and oxidization time is 0.5～2 hour.
3. preparation method according to claim 1 and 2, it is characterized in that, dropwise add sodium hydroxide solution that concentration is 0.1～1mol/L in the chlorauric acid solution that the solution that the described pH containing hydrochloro-auric acid solution is 7.0～8.0 is is 0.1～10mmol/L in concentration until the pH value is 7.0～8.0 obtained.
4. according to the described preparation method of any one in claim 1～3, it is characterized in that, in described step (3), with 1～5 ℃/min, be warming up to 100～650 ℃.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105836698A (en) * | 2016-04-15 | 2016-08-10 | 首都师范大学 | Preparation method of gold-titanium dioxide composite nano-tube array and gold nano-tube array electrode |
| CN105903074A (en) * | 2014-09-17 | 2016-08-31 | 上海施必康医疗器械有限公司 | Preparation method for active drug sustained-release coating on surface of craniomaxillofacial repairing titanium mesh |
| CN109745150A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院上海硅酸盐研究所 | A kind of bone implant and its preparation method and application having immunoloregulation function |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105903074A (en) * | 2014-09-17 | 2016-08-31 | 上海施必康医疗器械有限公司 | Preparation method for active drug sustained-release coating on surface of craniomaxillofacial repairing titanium mesh |
| CN105903074B (en) * | 2014-09-17 | 2018-09-14 | 上海施必康医疗器械有限公司 | Repair the preparation method of titanium net surface active drugs controlled-release coating in cranium jaw face |
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| CN109745150A (en) * | 2017-11-06 | 2019-05-14 | 中国科学院上海硅酸盐研究所 | A kind of bone implant and its preparation method and application having immunoloregulation function |
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