CN103469284B - The preparation method of a kind of carbon nano-tube/titanic oxide nano pipe biological composite coating material - Google Patents
The preparation method of a kind of carbon nano-tube/titanic oxide nano pipe biological composite coating material Download PDFInfo
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- CN103469284B CN103469284B CN201310347000.4A CN201310347000A CN103469284B CN 103469284 B CN103469284 B CN 103469284B CN 201310347000 A CN201310347000 A CN 201310347000A CN 103469284 B CN103469284 B CN 103469284B
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Abstract
The present invention relates to the preparation method of a kind of carbon nano-tube/titanic oxide nano pipe biological composite coating material, comprise the steps: first, utilize the Nano tube array of titanium dioxide coating that anonizing is neat in the preparation arrangement of Titanium board surface, caliber is 50-100nm; Then, utilize electrophoretic deposition even carbon nanotube to deposit to surface with on the Titanium base of Nano tube array of titanium dioxide. Compared with the Titanium board of smooth surface, compound coating prepared by the present invention improves the proliferation rate of human osteoblast cell on its surface.
Description
Technical field
The present invention relates to Materials science and biomedical crossing domain, in particular to a kind of taking surface with the titanium implant of even Nano tube array of titanium dioxide as matrix, have the preparation method of the biological composite coating of multi-walled carbon nano-tubes at its area load.
Background technology
In recent years, carbon nanotube makes it cause the extensive concern of people at biomedical sector with the physicochemical property of its excellence. Carbon nanotube mainly concentrates in biosensor, pharmaceutical carrier, biologic bracket material etc. in the application of biomedical sector. Carbon nanotube is used for timbering material and has obvious advantage: 1. specific tenacity height; 2. special one dimension Nano structure, is relatively applicable to building the environment of cell growth; 3. chemical property is stablized, and is easy to carry out finishing.
Titanium or titanium alloy becomes the preferred material of the human body hard tissue surrogates such as tooth implant, orthopedic steel plate and joint prosthesis with its good biocompatibility, low elastic modulus etc. that physical strength is close with chemical stability, erosion resistance and osseous tissue. But titanium or titanium alloy planting body itself belongs to bio-inert material, can be surrounded by one layer of packing tunica fibrosa after direct implant into body, it is difficult to very fast and matrix forms mortise, have impact on the success ratio of implantation. Therefore, in order to make, titanium or titanium alloy planting body has albumen in inductor, cell growth adheres to and bone growth, forms the bioactive functions that tight bone bond is closed, its surface is carried out modification very necessary.
Utilizing anonizing to prepare 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. Modified Nano tube array of titanium dioxide not only adds the specific surface area of material surface, and hollow tubular structure is also conducive to the absorption of biologically active substance.
Carbon nanotube is deposited on, by electrophoretic deposition process, the Titanium base surface that surface has Nano tube array of titanium dioxide coating, is expected to increase the adhesion of cell on surface, multiplication capacity, also be conducive to accelerating simultaneously hydroxyapatite its surface synthesis speed.
Summary of the invention
The present invention provides the preparation method of a kind of carbon nano-tube/titanic oxide nano pipe biological composite coating material, and described method comprises the steps:
1) the Nano tube array of titanium dioxide coating that anonizing is neat in the preparation arrangement of Titanium board surface, caliber is 50-100nm is utilized;
2) the multi-walled carbon nano-tubes suspension that electrolyte solution consists of carboxyl-functional is prepared;
3) to step 2) in obtained suspension carry out electrophoretic deposition, uniform loading carbon nanotube on the Titanium base of surface with Nano tube array of titanium dioxide.
Further, the concrete steps of described method are:
1) taking Pt metal sheet as negative electrode, the Titanium board that surface of polished is smooth is anode, the spacing of two electrodes is 1-2cm, is the solution Anodic Oxidation of ionogen at glycerol/Neutral ammonium fluoride/deionized water, voltage 20-40V, time 30-120min, take out, it is placed in deionized water and cleans, dry, 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 with titanium plate heating 450-550 DEG C of Nano tube array of titanium dioxide, after insulation 90-120min, furnace cooling;
3) get 100mg multi-walled carbon nano-tubes in round-bottomed flask, add in the mixing acid being made up of the vitriol oil and concentrated nitric acid, supersound process 30-60min, reflux 8-12h, cooling, is washed to neutrality, 60 DEG C of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
4) take dehydrated alcohol as solvent, by ultrasonic disperse mode by step 3) in the multi-walled carbon nano-tubes of carboxyl-functional that obtains make finely dispersed suspension;
5) taking Pt metal sheet as negative electrode, step 2) in the surface that obtains be anode with the titanium plate of Nano tube array of titanium dioxide, the spacing of two electrodes is 1-2cm, step 4) in the finely dispersed suspension that obtains be solution, electrophoretic deposition is carried out with voltage 20-40V, time 5-60s, slowly take out anode sample and naturally dry, namely obtain carbon nano-tube/titanic oxide nano pipe composite coating material.
Further, step 1) in the concentration of the Neutral ammonium fluoride that contains in glycerol electrolyte solution and water be respectively 1wt.% and 20wt.%.
Further, step 3) in the volume ratio of the vitriol oil and concentrated nitric acid be 3: 1.
Further, step 4) in the multi-walled carbon nano-tubes of every 10mg carboxyl-functional add in 100-200mL dehydrated alcohol.
Further, step 4) the ultrasonic disperse time is 30-60min.
The beneficial outcomes of the present invention is: 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 now the present invention more fully, show various embodiment. But, 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 is provided that these embodiments make the disclosure will be thoroughly with completely, and fully pass on the scope of the present invention to those skilled in the art.
[embodiment 1]
The time of electrophoretic deposition is 10s
(1) taking Pt metal sheet as negative electrode, the Titanium board that surface of polished is smooth is anode, the spacing of two electrodes is 1cm, at the solution Anodic Oxidation voltage 20V that glycerol/Neutral ammonium fluoride/deionized water is ionogen, time 60min, take out, it is placed in deionized water to clean, drying, obtains the titanium plate of surface with Nano tube array of titanium dioxide, and titania nanotube caliber is about 80nm;
(2) surface obtained in step (1) is heated to 500 DEG C with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) 100mg multi-walled carbon nano-tubes is got in round-bottomed flask, add (V sulfuric acid: V nitric acid=3: 1) in the mixing acid being made up of the vitriol oil and concentrated nitric acid, supersound process 30min, reflux 12h, cooling, being washed to neutrality, 60 DEG C of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) taking 200mL dehydrated alcohol as solvent, get in 10mg step (3) multi-walled carbon nano-tubes of the carboxyl-functional obtained, it is made into uniform suspension by the mode of ultrasonic disperse;
(5) taking 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, the spacing of two electrodes is 1cm, the finely dispersed suspension obtained in step (4) is solution, electrophoretic deposition is carried out with voltage 20V, time 10s, slowly take out anode sample and naturally dry, namely obtain carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material prepared by the present invention can reach: compared with the Titanium board of smooth surface, and the proliferation rate of human osteoblast cell on composite coating material surface increases by 21.6 �� 0.8%.
[embodiment 2]
The time of electrophoretic deposition is 20s
(1) taking Pt metal sheet as negative electrode, the Titanium board that surface of polished is smooth is anode, the spacing of two electrodes is 1cm, at the solution Anodic Oxidation voltage 20V that glycerol/Neutral ammonium fluoride/deionized water is ionogen, time 60min, take out, it is placed in deionized water to clean, drying, obtains the titanium plate of surface with Nano tube array of titanium dioxide, and titania nanotube caliber is about 80nm;
(2) surface obtained in step (1) is heated to 500 DEG C with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) 100mg multi-walled carbon nano-tubes is got in round-bottomed flask, add (V sulfuric acid: V nitric acid=3: 1) in the mixing acid being made up of the vitriol oil and concentrated nitric acid, supersound process 30min, reflux 12h, cooling, being washed to neutrality, 60 DEG C of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) taking 200mL dehydrated alcohol as solvent, get in 10mg step (3) multi-walled carbon nano-tubes of the carboxyl-functional obtained, it is made into uniform suspension by the mode of ultrasonic disperse;
(5) taking 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, the spacing of two electrodes is 1cm, the finely dispersed suspension obtained in step (4) is solution, electrophoretic deposition is carried out with voltage 20V, time 20s, slowly take out anode sample and naturally dry, namely obtain carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material prepared by the present invention can reach: compared with the Titanium board of smooth surface, and the proliferation rate of human osteoblast cell on composite coating material surface increases by 29.3 �� 0.5%.
[embodiment 3]
The time of electrophoretic deposition is 30s
(1) taking Pt metal sheet as negative electrode, the Titanium board that surface of polished is smooth is anode, the spacing of two electrodes is 1cm, at the solution Anodic Oxidation voltage 20V that glycerol/Neutral ammonium fluoride/deionized water is ionogen, time 60min, take out, it is placed in deionized water to clean, drying, obtains the titanium plate of surface with Nano tube array of titanium dioxide, and titania nanotube caliber is about 80nm;
(2) surface obtained in step (1) is heated to 500 DEG C with the titanium plate of Nano tube array of titanium dioxide, after insulation 120min, furnace cooling;
(3) 100mg multi-walled carbon nano-tubes is got in round-bottomed flask, add (V sulfuric acid: V nitric acid=3: 1) in the mixing acid being made up of the vitriol oil and concentrated nitric acid, supersound process 30min, reflux 12h, cooling, being washed to neutrality, 60 DEG C of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional;
(4) taking 200mL dehydrated alcohol as solvent, get in 10mg step (3) multi-walled carbon nano-tubes of the carboxyl-functional obtained, it is made into uniform suspension by the mode of ultrasonic disperse;
(5) taking 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, the spacing of two electrodes is 1cm, the finely dispersed suspension obtained in step (4) is solution, electrophoretic deposition is carried out with voltage 20V, time 30s, slowly take out anode sample and naturally dry, namely obtain carbon nano-tube/titanic oxide nano pipe composite coating material.
The salient features of the composite coating material prepared by the present invention can reach: compared with the Titanium board of smooth surface, and the proliferation rate of human osteoblast cell on composite coating material surface increases by 16.5 �� 0.7%.
The foregoing is only embodiments of the invention, it is not limited to the present invention. The present invention can have various suitable change and change. All do within the spirit and principles in the present invention any amendment, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. the preparation method of a carbon nano-tube/titanic oxide nano pipe biological composite coating material, it is characterised in that described method comprises the steps:
1) the Nano tube array of titanium dioxide coating that anonizing is neat in the preparation arrangement of Titanium board surface, caliber is 50-100nm is utilized;
2) the multi-walled carbon nano-tubes suspension that electrolyte solution consists of carboxyl-functional is prepared;
3) to step 2) in obtained suspension carry out electrophoretic deposition, uniform loading carbon nanotube on the Titanium base of surface 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, it is characterised in that the concrete steps of described method are:
1) taking Pt metal sheet as negative electrode, the Titanium board that surface of polished is smooth is anode, the spacing of two electrodes is 1-2cm, is the solution Anodic Oxidation of ionogen at glycerol/Neutral ammonium fluoride/deionized water, voltage 20-40V, time 30-120min, take out, it is placed in deionized water and cleans, dry, 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 DEG C with the titanium plate of Nano tube array of titanium dioxide, after insulation 90-120min, furnace cooling;
3) get 100mg multi-walled carbon nano-tubes in round-bottomed flask, add in the mixing acid being made up of the vitriol oil and concentrated nitric acid, supersound process 30-60min, reflux 8-12h, cooling, is washed to neutrality, 60 DEG C of vacuum-drying 24h, obtain the multi-walled carbon nano-tubes of carboxyl-functional
4) take dehydrated alcohol as solvent, by ultrasonic disperse mode by step 3) in the multi-walled carbon nano-tubes of carboxyl-functional that obtains make finely dispersed suspension;
5) taking Pt metal sheet as negative electrode, step 2) in the surface that obtains be anode with the titanium plate of Nano tube array of titanium dioxide, the spacing of two electrodes is 1-2cm, step 4) in the finely dispersed suspension that obtains be solution, electrophoretic deposition is carried out with voltage 20-40V, time 5-60s, slowly take out anode sample and naturally dry, namely obtain carbon nano-tube/titanic oxide nano pipe composite coating material.
3. preparation method according to claim 2, it is characterised in that: step 1) in the concentration of the Neutral ammonium fluoride that contains in glycerol electrolyte solution and water be respectively 1wt.% and 20wt.%.
4. preparation method according to claim 2, it is characterised 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, it is characterised in that: step 4) in the multi-walled carbon nano-tubes of every 10mg carboxyl-functional add in 100-200mL dehydrated alcohol.
6. preparation method according to claim 2, it is characterised in that: step 4) the ultrasonic disperse time is 30-60min.
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| 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 |
| WO2018118851A1 (en) * | 2016-12-19 | 2018-06-28 | 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 |
| 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 |
| 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 |
| CN113061942B (en) * | 2021-03-08 | 2023-11-03 | 常州大学 | Flexible super-hydrophobic surface preparation method based on carbon nano tube |
| CN113373493B (en) * | 2021-05-31 | 2022-11-18 | 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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