CN103469284A - Preparation method of carbon nanotube/titania nanotube bio-composite coat material - Google Patents
Preparation method of carbon nanotube/titania nanotube bio-composite coat material Download PDFInfo
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- CN103469284A CN103469284A CN2013103470004A CN201310347000A CN103469284A CN 103469284 A CN103469284 A CN 103469284A CN 2013103470004 A CN2013103470004 A CN 2013103470004A CN 201310347000 A CN201310347000 A CN 201310347000A CN 103469284 A CN103469284 A CN 103469284A
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Abstract
The invention relates to a preparation method of a carbon nanotube/titania nanotube bio-composite coat material. The preparation method comprises the following steps: preparing an aligned titania nanotube array coat having a caliber of 50-100nm on the surface of a pure titanium plate through utilizing an anodization process; and uniformly depositing functionalized multi-wall carbon nanotubes on a titanium matrix with the surface having a titania nanotube array through utilizing an electrophoretic deposition process. The reproduction rate of human osteoblast on the surface of the composite coat prepared in the invention is higher than the reproduction rate of the human osteoblast on the pure titanium plate having a smooth surface.
Description
Technical field
The present invention relates to Materials science and biomedical crossing domain, particularly a kind of to take surface be matrix with the even titanium implant of Nano tube array of titanium dioxide, and the preparation method of the biological composite coating of multi-walled carbon nano-tubes is arranged at its area load.
Background technology
In recent years, the carbon nanotube physicochemical property excellent with it make it cause people's extensive concern at biomedical sector.Carbon nanotube mainly concentrates on the aspects such as biosensor, pharmaceutical carrier, biologic bracket material in the application of biomedical sector.Carbon nanotube has obvious advantage for timbering material: 1. specific tenacity is high; 2. special one dimension Nano structure, be applicable to building the environment of Growth of Cells; 3. stable chemical nature, be easy to carry out finishing.
The biocompatibility that titanium or titanium alloy is good with it, physical strength and chemical stability, erosion resistance, low elastic modulus close with osseous tissue etc. become the preferred material of the human body hard tissue surrogates such as tooth implant, orthopedic steel plate and joint prosthesis.But titanium or titanium alloy planting body itself belongs to bio-inert material, directly after implant into body, can be surrounded by one deck packing tunica fibrosa, be difficult to very fast and matrix formation mortise, affected the success ratio of implanting.Therefore, for making the titanium or titanium alloy planting body, there is albumen in inductor, Growth of Cells adhesion and bone growth, form the bioactive functions that tight bone bond is closed, very necessary to its modifying surface.
Utilizing anonizing to prepare the Nano tube array of titanium dioxide coating at titanium implant surface is the surface modifying method that a kind of technique is simple, with low cost, controllability is strong.Nano tube array of titanium dioxide after modification has not only increased the specific surface area of material surface, and hollow tubular structure also is conducive to the absorption of biologically active substance.
Carbon nanotube is deposited on to the titanium matrix surface that surface has the Nano tube array of titanium dioxide coating by electrophoretic deposition process, is expected to increase cell at surperficial adhesion, multiplication capacity, also be conducive to accelerate simultaneously hydroxyapatite its surface formation speed.
Summary of the invention
The invention provides a kind of preparation method of carbon nano-tube/titanic oxide nano pipe biological composite coating material, described method comprises the steps:
At first, utilize the Nano tube array of titanium dioxide coating that anonizing is 50-100nm at pure titanium plate surface preparation marshalling, caliber; Then, utilize electrophoretic deposition by the multi-walled carbon nano-tubes uniform deposition of carboxyl-functional to surface on the titanium matrix with Nano tube array of titanium dioxide.
Further, the concrete steps of described method are:
1) take the Pt metal sheet as negative electrode, the pure titanium plate that surface of polished is smooth is anode, between two electrodes, distance is 1-2cm, at glycerol/Neutral ammonium fluoride/deionized water, is electrolytical solution Anodic Oxidation, voltage 20-40V, time 30-120min, take out, be placed in deionized water and clean, drying, obtain the titanium plate of surface with Nano tube array of titanium dioxide, the average caliber 50-100nm of titania nanotube;
2) by step 1) in the surface that obtains be heated to 450-550 ℃ with the titanium plate of Nano tube array of titanium dioxide, after insulation 90-120min, furnace cooling;
3) get the 100mg multi-walled carbon nano-tubes in round-bottomed flask, add in the mixing acid formed by the vitriol oil and concentrated nitric acid supersound process 30-60min, reflux 8-12h, cooling, be washed to neutrality, 60 ℃ of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
4) take dehydrated alcohol as solvent, with ultrasonic dispersing mode by step 3) in the multi-walled carbon nano-tubes of the carboxyl-functional that obtains make finely dispersed suspension;
5) take the Pt metal sheet as negative electrode, step 2) surface obtained in is anode with the titanium plate of Nano tube array of titanium dioxide, between two electrodes, distance is 1-2cm, step 4) the finely dispersed suspension obtained in is solution, carry out electrophoretic deposition with voltage 20-40V, time 5-60s, slowly take out the anode sample and naturally dry, and obtains carbon nano-tube/titanic oxide nano pipe composite coating material.
Further, the Neutral ammonium fluoride contained in the glycerol electrolyte solution step 1) and the concentration of water are respectively 1wt.% and 20wt.%.
Further, step 3), the volume ratio of the vitriol oil and concentrated nitric acid is 3: 1.
Further, step 4), the multi-walled carbon nano-tubes of every 10mg carboxyl-functional adds in the 100-200mL dehydrated alcohol.
Further, step 4) ultrasonic jitter time is 30-60min.
Useful result of the present invention is: the human osteoblast cell increases in adhesion, the multiplication rate of carbon nano-tube/titanic oxide nano pipe biological composite coating material surface.
Embodiment
Hereinafter, will describe more fully the present invention now, show various embodiment.Yet the present invention can implement in many different forms, and should not be interpreted as being confined to embodiment set forth herein.On the contrary, it will be thorough with completely providing these embodiment to make the disclosure, and scope of the present invention is conveyed to those skilled in the art fully.
[embodiment 1]
The time of electrophoretic deposition is 10s
(1) take the Pt metal sheet as negative electrode, the pure titanium plate that surface of polished is smooth is anode, between two electrodes, distance is 1cm, at glycerol/Neutral ammonium fluoride/deionized water, be electrolytical solution Anodic Oxidation voltage 20V, time 60min, take out, being placed in deionized water cleans, drying, obtain the titanium plate of surface with Nano tube array of titanium dioxide, and the titania nanotube caliber is about 80nm;
(2) surface that obtains in step (1) is heated to 500 ℃ with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) get the 100mg multi-walled carbon nano-tubes in round-bottomed flask, add (V in the mixing acid formed by the vitriol oil and concentrated nitric acid
sulfuric acid: V
nitric acid=3: 1), supersound process 30min, reflux 12h, cooling, be washed to neutrality, 60 ℃ of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) take the 200mL dehydrated alcohol as solvent, get the multi-walled carbon nano-tubes of the carboxyl-functional obtained in 10mg step (3), by the mode of ultrasonic dispersion, be made into uniform suspension;
(5) take the Pt metal sheet as negative electrode, the surface obtained in step (2) is anode with the titanium plate of Nano tube array of titanium dioxide, between two electrodes, distance is 1cm, the finely dispersed suspension obtained in step (4) is solution, carry out electrophoretic deposition with voltage 20V, time 10s, slowly take out the anode sample and naturally dry, and obtains carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material that the present invention is prepared can reach: with ganoid pure titanium plate, compare, the human osteoblast cell increases by 21.6 ± 0.8% at the proliferation rate on composite coating material surface.
[embodiment 2]
The time of electrophoretic deposition is 20s
(1) take the Pt metal sheet as negative electrode, the pure titanium plate that surface of polished is smooth is anode, between two electrodes, distance is 1cm, at glycerol/Neutral ammonium fluoride/deionized water, be electrolytical solution Anodic Oxidation voltage 20V, time 60min, take out, being placed in deionized water cleans, drying, obtain the titanium plate of surface with Nano tube array of titanium dioxide, and the titania nanotube caliber is about 80nm;
(2) surface that obtains in step (1) is heated to 500 ℃ with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) get the 100mg multi-walled carbon nano-tubes in round-bottomed flask, add (V in the mixing acid formed by the vitriol oil and concentrated nitric acid
sulfuric acid: V
nitric acid=3: 1), supersound process 30min, reflux 12h, cooling, be washed to neutrality, 60 ℃ of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) take the 200mL dehydrated alcohol as solvent, get the multi-walled carbon nano-tubes of the carboxyl-functional obtained in 10mg step (3), by the mode of ultrasonic dispersion, be made into uniform suspension;
(5) take the Pt metal sheet as negative electrode, the surface obtained in step (2) is anode with the titanium plate of Nano tube array of titanium dioxide, between two electrodes, distance is 1cm, the finely dispersed suspension obtained in step (4) is solution, carry out electrophoretic deposition with voltage 20V, time 20s, slowly take out the anode sample and naturally dry, and obtains carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material that the present invention is prepared can reach: with ganoid pure titanium plate, compare, the human osteoblast cell increases by 29.3 ± 0.5% at the proliferation rate on composite coating material surface.
[embodiment 3]
The time of electrophoretic deposition is 30s
(1) take the Pt metal sheet as negative electrode, the pure titanium plate that surface of polished is smooth is anode, between two electrodes, distance is 1cm, at glycerol/Neutral ammonium fluoride/deionized water, be electrolytical solution Anodic Oxidation voltage 20V, time 60min, take out, being placed in deionized water cleans, drying, obtain the titanium plate of surface with Nano tube array of titanium dioxide, and the titania nanotube caliber is about 80nm;
(2) surface that obtains in step (1) is heated to 500 ℃ with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) get the 100mg multi-walled carbon nano-tubes in round-bottomed flask, add (V in the mixing acid formed by the vitriol oil and concentrated nitric acid
sulfuric acid: V
nitric acid=3: 1), supersound process 30min, reflux 12h, cooling, be washed to neutrality, 60 ℃ of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) take the 200mL dehydrated alcohol as solvent, get the multi-walled carbon nano-tubes of the carboxyl-functional obtained in 10mg step (3), by the mode of ultrasonic dispersion, be made into uniform suspension;
(5) take the Pt metal sheet as negative electrode, the surface obtained in step (2) is anode with the titanium plate of Nano tube array of titanium dioxide, between two electrodes, distance is 1cm, the finely dispersed suspension obtained in step (4) is solution, carry out electrophoretic deposition with voltage 20V, time 30s, slowly take out the anode sample and naturally dry, and obtains carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material that the present invention is prepared can reach: with ganoid pure titanium plate, compare, the human osteoblast cell increases by 16.5 ± 0.7% at the proliferation rate on composite coating material surface.
The foregoing is only embodiments of the invention, be not limited to the present invention.The present invention can have various suitable changes and variation.All any modifications of doing within the spirit and principles in the present invention, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (6)
1. the preparation method of a carbon nano-tube/titanic oxide nano pipe biological composite coating material, is characterized in that described method comprises the steps:
At first, utilize the Nano tube array of titanium dioxide coating that anonizing is 50-100nm at pure titanium plate surface preparation marshalling, caliber; Then, utilize electrophoretic deposition by the multi-walled carbon nano-tubes uniform deposition of carboxyl-functional to surface on the titanium matrix with Nano tube array of titanium dioxide.
2. the preparation method of a kind of carbon nano-tube/titanic oxide nano pipe biological composite coating material as claimed in claim 1 is characterized in that the concrete steps of described method are:
1) take the Pt metal sheet as negative electrode, the pure titanium plate that surface of polished is smooth is anode, between two electrodes, distance is 1-2cm, at glycerol/Neutral ammonium fluoride/deionized water, is electrolytical solution Anodic Oxidation, voltage 20-40V, time 30-120min, take out, be placed in deionized water and clean, drying, obtain the titanium plate of surface with Nano tube array of titanium dioxide, the average caliber 50-100nm of titania nanotube;
2) by step 1) in the surface that obtains be heated to 450-550 ℃ with the titanium plate of Nano tube array of titanium dioxide, after insulation 90-120min, furnace cooling;
3) get the 100mg multi-walled carbon nano-tubes in round-bottomed flask, add in the mixing acid formed by the vitriol oil and concentrated nitric acid supersound process 30-60min, reflux 8-12h, cooling, be washed to neutrality, 60 ℃ of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
4) take dehydrated alcohol as solvent, with ultrasonic dispersing mode by step 3) in the multi-walled carbon nano-tubes of the carboxyl-functional that obtains make finely dispersed suspension;
5) take the Pt metal sheet as negative electrode, step 2) surface obtained in is anode with the titanium plate of Nano tube array of titanium dioxide, between two electrodes, distance is 1-2cm, step 4) the finely dispersed suspension obtained in is solution, carry out electrophoretic deposition with voltage 20-40V, time 5-60s, slowly take out the anode sample and naturally dry, and obtains carbon nano-tube/titanic oxide nano pipe composite coating material.
3. preparation method according to claim 2, is characterized in that: step 1) in the Neutral ammonium fluoride that contains in the glycerol electrolyte solution and the concentration of water be respectively 1wt.% and 20wt.%.
4. preparation method according to claim 2, is characterized in that: step 3) in the volume ratio of the vitriol oil and concentrated nitric acid be 3: 1.
5. preparation method according to claim 2, is characterized in that: step 4) in the multi-walled carbon nano-tubes of every 10mg carboxyl-functional add in the 100-200mL dehydrated alcohol.
6. preparation method according to claim 2, is characterized in that: step 4) ultrasonic jitter time is 30-60min.
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Cited By (8)
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| CN106563176A (en) * | 2016-10-14 | 2017-04-19 | 湖北大学 | Atomic layer deposition-based preparation method for zinc oxide/carbon nanotube nano-antibacterial coating |
| CN107019571A (en) * | 2017-06-02 | 2017-08-08 | 南方医科大学 | A kind of method that selective laser melting prepares dentistry implant |
| CN108256286A (en) * | 2018-01-10 | 2018-07-06 | 内蒙古工业大学 | Amphoteric water-soluble catalyst aerobic oxidation benzyl alcohol is into the study on mechanism analysis method of benzaldehyde |
| CN109382083A (en) * | 2018-11-30 | 2019-02-26 | 内蒙古工业大学 | Carbon nano tube-doped titania nanotube catalysis material and preparation method thereof |
| CN113061942A (en) * | 2021-03-08 | 2021-07-02 | 常州大学 | Preparation method of flexible super-hydrophobic surface based on carbon nano tube |
| CN113373493A (en) * | 2021-05-31 | 2021-09-10 | 南京理工大学 | Preparation method of carbon nanotube reinforced fiber metal laminate |
| CN114551110A (en) * | 2022-02-23 | 2022-05-27 | 青岛大学 | Cut carbon nanotube @ TiO2Nanotube array heterostructure and preparation method and device thereof |
| US11433375B2 (en) * | 2016-12-19 | 2022-09-06 | University Of Cincinnati | Photocatalytic carbon filter |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106563176A (en) * | 2016-10-14 | 2017-04-19 | 湖北大学 | Atomic layer deposition-based preparation method for zinc oxide/carbon nanotube nano-antibacterial coating |
| CN106563176B (en) * | 2016-10-14 | 2019-04-30 | 湖北大学 | A kind of preparation method of the zinc oxide based on atomic layer deposition/carbon nanotube antimicrobial coating |
| US11433375B2 (en) * | 2016-12-19 | 2022-09-06 | University Of Cincinnati | Photocatalytic carbon filter |
| CN107019571A (en) * | 2017-06-02 | 2017-08-08 | 南方医科大学 | A kind of method that selective laser melting prepares dentistry implant |
| CN108256286A (en) * | 2018-01-10 | 2018-07-06 | 内蒙古工业大学 | Amphoteric water-soluble catalyst aerobic oxidation benzyl alcohol is into the study on mechanism analysis method of benzaldehyde |
| CN108256286B (en) * | 2018-01-10 | 2021-07-02 | 内蒙古工业大学 | Research and analysis method for reaction mechanism of aerobic oxidation of benzyl alcohol into benzaldehyde by using amphoteric water-soluble catalyst |
| CN109382083A (en) * | 2018-11-30 | 2019-02-26 | 内蒙古工业大学 | Carbon nano tube-doped titania nanotube catalysis material and preparation method thereof |
| CN109382083B (en) * | 2018-11-30 | 2021-07-20 | 内蒙古工业大学 | Carbon nanotube-doped titanium dioxide nanotube photocatalytic material and preparation method thereof |
| CN113061942A (en) * | 2021-03-08 | 2021-07-02 | 常州大学 | Preparation method of flexible super-hydrophobic surface based on carbon nano tube |
| CN113061942B (en) * | 2021-03-08 | 2023-11-03 | 常州大学 | Flexible super-hydrophobic surface preparation method based on carbon nano tube |
| CN113373493A (en) * | 2021-05-31 | 2021-09-10 | 南京理工大学 | Preparation method of carbon nanotube reinforced fiber metal laminate |
| CN114551110A (en) * | 2022-02-23 | 2022-05-27 | 青岛大学 | Cut carbon nanotube @ TiO2Nanotube array heterostructure and preparation method and device thereof |
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