CN102677055B - Nano composite material based on titanium metal surface and preparation method thereof - Google Patents
Nano composite material based on titanium metal surface and preparation method thereof Download PDFInfo
- Publication number
- CN102677055B CN102677055B CN 201210209846 CN201210209846A CN102677055B CN 102677055 B CN102677055 B CN 102677055B CN 201210209846 CN201210209846 CN 201210209846 CN 201210209846 A CN201210209846 A CN 201210209846A CN 102677055 B CN102677055 B CN 102677055B
- Authority
- CN
- China
- Prior art keywords
- preparation
- metal titanium
- graphite
- film
- titanium oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a nano composite material based on a titanium metal surface, which comprises the following steps: carrying out carbon plasma immersion ion implantation and deposition on a regular titanium oxide nanotube array film on a titanium metal surface, thereby forming a graphite/titanium oxide composite film with a nano hollow conical array on the titanium metal surface. The invention implements preparation of the graphite/titanium oxide composite nano material, and solves the problem of single component and structural composition in the nano titanium oxide film material generated by in-situ oxidization on the titanium metal surface in the prior art.
Description
Technical field
The present invention relates to a kind of method for preparing nano composite material based on surface of metal titanium, specifically, relate to a kind of anodizing technology and plasma immersion ion injection and deposition technique recombining process of using and have the method for the graphite/titanium oxide composite film of hollow nano tapered array structure in the surface of metal titanium preparation, belong to nano material preparation and metal surface properties modification technical field.
Background technology
Titania meterial is because have good erosion resistance, and biocompatibility, excellent electricity and characteristic of semiconductor be at material protection, biomedicine, and semiconducter device and photochemical catalysis, the numerous areas such as environment protection are studied widely and are used.The titanium oxide nanotubes thin-film material had both had the functional of material itself, the tubulose geometry that has again nanoscale, have simultaneously the performance anisotropy, prepare the characteristics such as simple, make it as the in-depth of the new functional type nano film material of a class and widen research and application in each field.
Anodizing technology is due to the equipment of cheapness, and the simple controlled advantages such as technique are widely used in metal material surface and modify and modification.Zwilling (Surface and Interface Analysis 1999,27 (7): 629-637.) etc. the people finds that in fluorine-containing electrolytic solution, the anodic oxidation of titanium base material can generate the nanometer porous titanium oxide film in its surface in situ oxidation, make anodizing technology become the technical way that generates the nanophase titania films material based on titanium substrate surface in-situ oxidation.By a series of processing parameter adjustment, can realize the preparation of the regular titania nanotube array film of surface of metal titanium.
Plasma immersion ion injects and deposition (Plasma immersion ion implantation and deposition, PIII﹠amp; D) technology is a kind of novel surface modified method of being used widely in recent years, its ultimate principle is the pending sample of low-temperature plasma submergence that produces, be set in sample surfaces by extraneous bias voltage and realize high-octane ion implantationly, utilize the diffusion of ion and the generation that the energy cohesion realizes the compound and surface nano-structure of sample surfaces composition multielement easily.The people such as Lifshitz studies show that and inject the forming core be beneficial to nano surface crystal grain by high energy ion (Science 2002,297 (5586): 1531-1533.).Compare with other process for modifying surface, plasma immersion ion injects and has advantages of uniqueness: ion implantation process is the thermal nonequilibrium process, is not subjected to the restriction of metallurgy rule, can realize that the injection of most of ions is carried out modification and modification to sample surfaces; Simultaneously ion implantation process is instantaneous heat-processed, can the atarting material internal structure, the variation of composition and external shape; In addition, PIII﹠amp; The D technology has high reaction activity and omnibearing characteristics, can effectively carry out uniform ion implantation and deposition to heterotypic material, be fit to have the injection process of the material of complicated shape, overcome the shortcoming that the conventional ion implantttion technique can only be carried out " sight line injection ".
Yet the single the Nomenclature Composition and Structure of Complexes feature of the material system of titanium oxide nanotubes thin-film material still can not satisfy new functional design demand.Therefore, form single problem in order to solve nanophase titania films material composition and the structure that in prior art, the surface of metal titanium in-situ oxidation generates, how to realize the nanometer of material system, Composite is to realize that its functionalization is the key issue in novel material design and preparation.
Summary of the invention
The problems referred to above in the face of the prior art existence, the present invention is intended to by nanoscale special construction design on implementation structure simultaneously and forms the recombining process of upper nanocrystal matrix material preparation, provides that a kind of preparation has the method for the graphite/titanium oxide composite film of hollow nano tapered array structure based on surface of metal titanium.
The invention provides a kind of preparation method who prepares nano composite material based on surface of metal titanium, possess following steps: the regular titania nanotube array film to surface of metal titanium carries out the injection of carbon plasma immersion ion and depositing treatment technique, forms the graphite/titanium oxide composite film with hollow nano tapered array in surface of metal titanium with this.
In the present invention, preferably carry out that the carbon plasma immersion ion injects or during depositing treatment take high purity graphite as negative electrode.Graphite is originated with carbon element as experiment, and characteristics that be easy to shape cheap because of it are found broad application; High purity graphite has the high purity characteristics, can form evenly high-density monovalence carbonium ion plasma body after washing from of passages through which vital energy circulates.This carbon plasma has simple behavioural characteristic and has the advantages that to control under the effect of magnetic field and electric field, be conducive to nucleation and the growth of surface carbon tapered hollow structure.
In the present invention, being preferably at the base vacuum degree is 3.0 * 10
-3～5.0 * 10
-3Pa, injecting voltage are that 15 ~ 40kV, pulse-repetition are that 5 ~ 9Hz, pulsewidth are that 200 ~ 500 μ s, injection length are under the processing condition of 30 ~ 120 minutes, utilize described plasma immersion ion to inject treatment process and the regular titania nanotube array film on titanium metal top layer is entered carbon ion inject.Like this, can make carbon laydown at the nanometer mouth of pipe, obtain the titanium oxide nanotubes film of carbon containing.
Described plasma immersion ion depositing treatment optimal process is 3.0 * 10 at the base vacuum degree
-3～5.0 * 10
-3Pa, pulsed voltage are that 200～600V, pulse-repetition are that 5 ~ 9Hz, pulsewidth are that 1000～4000 μ s, dutycycle are 10% ~ 30%, depositing time is to carry out under the processing condition of 30～120 minutes.
To carry out through the carbon containing titanium oxide nanotubes film that plasma immersion ion Implantation ion processing surface of metal titanium obtains the plasma immersion ion depositing treatment can make carbon laydown at nanotube interruption-forming ring-type rete.Again, described ring-type rete forms for successively generating.Formation due to the outer plasma sheath of its special surface structure impact of titanium oxide nanotubes, carbon ion is subject to this asymmetric sheath layer disturbing influence, axial dipole field appears in the annular membrane of layer by layer deposition growth, and its carbocyclic ring diameter reduces gradually, finally forms the tapered hollow structure in nanotube surface.
The present invention utilizes plasma immersion ion to inject and deposition technique, and described carbon ion injects and carries out the carbon ion deposition on regular titania nanotube array film, and regular titania nanotube array pattern is replaced by nanometer taper array of structures fully.Obtain the graphite/titanium oxide composite film with hollow nano tapered array in surface of metal titanium formation.Surface of metal titanium is processed the titanium oxide nanotubes film that obtains through anodizing technology, its surface presents super water-wet behavior; After carrying out carbon plasma injection or deposition technique processing, according to the difference of degree for the treatment of, can realize progressively that film surface is from super hydrophilic transformation to hydrophobic process.The characteristic of utilizing this hydrophilic and hydrophobic to change, laminated film can be applied to the automatically cleaning field; Simultaneously graphite/titanium oxide is compound can realize the photocatalysis of titania meterial in visible-range, may be studied and use in environment protection such as sewage disposal and outdoor anti-pollution layer or film field.
In preparation method of the present invention, adopt anodizing technology at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.The method is the effective way that obtains independent nano-pipe array thin film, and the Ti sheet that breaks away from after array can directly be utilized again.In addition, preferably, described oxidation voltage is 30～80V, and oxidization time is 5～15 hours.Can make better complete, independent, orderly nano-pipe array thin film like this on the titanium metal base, and geomery is controlled.
The present invention carries out the carbon plasma immersion ion by the regular titania nanotube array film to surface of metal titanium and injects processing and depositing treatment, can form the graphite/titanium oxide composite film with hollow nano tapered array structure in surface of metal titanium, its constitutional features is nanometer taper array, its surface presents hydrophobic property, and the carbon plasma technical finesse realizes that the film surface hydrophilic and hydrophobic changes; Be combined with nano-tube array simultaneously to consist of and seal hollow structure, may be applied to the loading of medicine and transport.Preferably form described graphite/the titanium oxide composite film component is TiOx nano crystal grain and the amorphous graphite of graphite and Detitanium-ore-type, graphite/the titanium oxide composite film of crystallization can effectively reduce the energy gap of titanium oxide, realization is applied in photochemical catalysis and environmental pollution improvement field in the photocatalysis of visible-range.
The present invention realizes the preparation of graphite/titanium oxide composite nano materials, solves nanophase titania films material composition and the structure that in prior art, the surface of metal titanium in-situ oxidation generates and forms single problem.
Description of drawings
Fig. 1 illustrates the pretreated surface of metal titanium shape appearance figure of process of the present invention;
Fig. 2 a illustrates the surface of metal titanium shape appearance figure through anodic oxidation treatment of the present invention, and interior illustration is the high power shape appearance figure;
Fig. 2 b illustrates through anodic oxidation of the present invention and plasma immersion ion and injects the surface of metal titanium shape appearance figure of processing, and interior illustration is the high power shape appearance figure;
Fig. 2 c illustrates through anodic oxidation of the present invention and plasma immersion ion injects and the surface of metal titanium shape appearance figure of depositing treatment, and interior illustration is the high power shape appearance figure;
Fig. 2 d illustrates the surface topography map with hollow nano tapered array structure composite film that obtains through the surface of metal titanium that anodic oxidation of the present invention and plasma immersion ion inject and the deposition recombining process is processed, and interior illustration is the high power shape appearance figure;
Fig. 3 illustrates through recombining process of the present invention and processes the side shape appearance figure with hollow nano tapered array structure composite film that obtains after surface of metal titanium;
Fig. 4 illustrates through recombining process of the present invention and processes the cross section transmission electron micrograph with hollow nano tapered array structure composite film that obtains after surface of metal titanium, and interior inserting photograph is electron diffraction pattern (lower-left) and regional area magnification at high multiple picture (upper right);
Fig. 5 a illustrates zero kinetic energy spectroscopy (XPS) figure with the surperficial titanium elements of hollow nano pyramidal structure laminated film that obtains after recombining process of the present invention is processed surface of metal titanium;
Fig. 5 b illustrates zero kinetic energy spectroscopy (XPS) figure with hollow nano pyramidal structure laminated film surface carbon element that obtains after recombining process of the present invention is processed surface of metal titanium;
Fig. 6 illustrates through recombining process of the present invention and processes the Raman collection of illustrative plates with hollow nano pyramidal structure laminated film surface that obtains after surface of metal titanium.
Embodiment
The present invention utilizes graphite/titanium oxide composite film that anodizing technology and plasma immersion ion inject and the deposition technique recombining process has hollow nano tapered array structure in the surface of metal titanium preparation.With reference to Figure of description, and further illustrate with the following embodiments the present invention, should be understood that following embodiment only is used for explanation the present invention, and unrestricted the present invention.
The present invention is to provide a kind of method for preparing nano composite material based on surface of metal titanium, comprise: the regular titania nanotube array film to surface of metal titanium carries out the injection of carbon plasma immersion ion and depositing treatment, with this step at the graphite/titanium oxide composite film with hollow nano tapered array of surface of metal titanium formation.
In the present invention, can use anodizing technology at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.The processing condition of anodizing technology and parameter can be: electrolytic solution is the ethylene glycol mixing solutions, and oxidation voltage is 20 ~ 80V, and oxidization time is 1 ~ 96h.Preferred processing condition and parameter are: electrolytic solution is the ethylene glycol mixing solutions, wherein contains mass percent and be 0.25% Neutral ammonium fluoride and volume percent and be 1% ultrapure water, and oxidation voltage is 30 ~ 60V, and oxidization time is 5 ~ 50h.
When using plasma immersion ion to inject and deposition technique carries out on above-mentioned regular titania nanotube array film surface that carbon ion injects or during deposition, preferably take high purity graphite as negative electrode.
Carrying out the processing parameter of carbon ion when injecting on regular titania nanotube array film surface is: the base vacuum degree is 3.0 * 10
-3～5.0 * 10
-3Pa, injecting voltage are 15 ~ 40kV, and pulse-repetition is 5 ~ 9Hz, and pulsewidth is 200 ~ 500 μ s, and injection length is 30 ~ 120 minutes; Preferred processing condition and parameter are: the base vacuum degree is 4.0 * 10
-3Pa, injecting voltage are 20kV, and pulse-repetition is 8Hz, and pulsewidth is 450 μ s, and injection length is 60 minutes.
Injecting regular titania nanotube array film surface at carbon carries out the processing parameter of carbon ion deposition and be: the base vacuum degree is 3.0 * 10
-3～5.0 * 10
-3Pa, pulsed voltage is 200～600V, and pulse-repetition is 5 ~ 9Hz, and pulsewidth is 1000～4000 μ s, and dutycycle is 10% ~ 30%, depositing time is 30～120 minutes; Preferred deposition process parameters is: the base vacuum degree is 4.0 * 10
-3Pa, pulsed voltage is 450V, and pulse-repetition is 8Hz, and pulsewidth is 2000 μ s, and dutycycle is 15%, depositing time is 30～120 minutes.
After recombining process of the present invention was processed, the surface of metal titanium original position generated the graphite/titanium oxide composite film with hollow nano tapered array structure, its three-dimensional structure be the titanium oxide nanotubes matrix in conjunction with the coniform cap of graphite, form the nano-array of hollow; Component is graphite and anatase-type titanium oxide and the unbodied graphite of nanocrystal.
Compared with prior art, the present invention has following beneficial effect: through the surface of metal titanium of recombining process processing of the present invention, it is a kind of graphite/titanium oxide composite film with hollow nano tapered array structure, its constitutional features is nanometer taper array, be combined with nano-tube array to consist of and seal hollow structure, component is TiOx nano crystal grain and the amorphous graphite of graphite and Detitanium-ore-type.Simultaneously nanoscale special construction design and form upper nanocrystal matrix material preparation on implementation structure of recombining process of the present invention.
The below further exemplifies embodiment to describe exemplary process of the present invention in detail.Should be understood that following embodiment is for the present invention is described better, and unrestricted the present invention.The raw material that adopts, reagent can marketable material or traditional chemical transform mode are synthetic to be made by buying.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, is for example " condition in the smooth organic chemistry handbook of Bel Si (Chemical Industry Press, 1996), or the condition of advising according to manufacturer.Unless stated otherwise, ratio and per-cent are based on molar mass.Unless otherwise defined or explanation, same meanings of being familiar with of all specialties used herein and scientific words and those skilled in the art.Any or method and material that be equal to similar to described content all can be applicable in the inventive method in addition.Other aspects of the present invention due to the disclosure of this paper, are that appearance is intelligible to those skilled in the art.
(1) after the pure titanium metal sheet process polished finish with 10mm * 10mm * 1mm, use successively acetone, alcohol and deionized water ultrasonic cleaning clean, each 15 minutes, obtain clean uniform surperficial (see figure 1).Adopt anodizing technology, at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.Concrete technology condition and parameter are shown in Table 1.The surface topography map that obtains under this processing parameter is seen shown in Fig. 2 a, the nano-tube array structure of result demonstration surface of metal titanium formation rule;
Table 1 anode oxidation process condition and parameter
(2) to after processing regular titania nanotube array film that surface of metal titanium obtains through above-mentioned anodizing technology and carrying out drying treatment, using plasma immersion ion implantttion technique, take high purity graphite as negative electrode, regular titania nanotube array film to surface of metal titanium carries out the carbon ion injection, obtains the titanium oxide nanotubes film of carbon containing.Concrete injection parameter is shown in Table 2; The surface topography map that obtains under this injection parameter sees shown in Fig. 2 b, and result shows that the tube wall at nanometer mouth of pipe place thickens, and shows that carbon is arranged is salty long-pending at nanotube:
Table 2 carbon ion injection parameter
。
(3) the above-mentioned carbon containing titanium oxide nanotubes film that obtains through anodizing technology and plasma immersion ion Implantation ion processing surface of metal titanium is carried out the plasma immersion ion depositing treatment.Concrete carbon ion deposition parameter is shown in Table 3.The surface topography map that obtains under this deposition parameter is seen shown in Fig. 2 c, find the titanium oxide nanotubes surface topography generation considerable change afterwards of carbon ion deposition by scanning electron microscopic observation: the nanometer mouth of pipe has carbon laydown to form the ring-type rete, and progressively upwards growth, and interior ring diameter progressively dwindles; At the carbon film outer wall, the successively vestige of growth is arranged clearly;
Table 3 carbon ion deposition parameter
The present embodiment step (1) and (2) are same as embodiment 1, description is omitted.(3) will carry out the plasma immersion ion depositing treatment through the carbon containing titanium oxide nanotubes film that above-described embodiment 1 anodizing technology and plasma immersion ion Implantation ion processing surface of metal titanium obtain.Concrete carbon ion deposition parameter is shown in Table 4; The surface topography map that obtains under this deposition parameter sees shown in Fig. 2 d, and result shows that regular titania nanotube array pattern is replaced by nanometer taper array of structures fully.The cap that single nanotube top and carbon laydown plated film form taper consists of enclosed construction, but can find out that from the part damaged part nanometer taper cap in top keeps hollow structure, as shown in Figure 3.Do cross section transmission electron microscopy sign to having hollow nano tapered array structure composite film, as shown in Figure 4, the light and shade striped of sample bottom rule is the regular nano tube structure that forms, the lines that the top has obvious carbon laydown film successively to grow and stay, there is a large amount of particles to occur at its combining site, shows it is the nanocrystal of graphite and titanium oxide by choosing electron diffraction and high magnification amplification picture:
Table 4 carbon ion deposition parameter
Graphite/the titanium oxide composite film with hollow nano tapered array structure that will obtain after above-described embodiment 2 anodizing technologies and plasma immersion ion injection and deposition technique recombining process processing surface of metal titanium carries out X ray photoelectron spectroscopy and detects.Fig. 5 a is the high resolution XPS collection of illustrative plates of the graphite with the hollow nano tapered array structure/titanium oxide composite film surface titanium elements after above-described embodiment 4 recombining process are processed surface of metal titanium, and Fig. 5 b is the high resolution XPS collection of illustrative plates of the graphite with hollow nano tapered array structure/titanium oxide composite film surface carbon element after above-described embodiment 4 recombining process are processed surface of metal titanium.By in figure as can be known, surperficial titanium elements mainly exists with the form of titanium oxide, and carbon exists two kinds of forms of crystalline graphite and non-crystalline graphite to exist.
Graphite/the titanium oxide composite film with hollow nano tapered array structure that will obtain after above-described embodiment 2 anodizing technologies and plasma immersion ion injection and deposition technique recombining process processing surface of metal titanium carries out Surface Raman Spectra and detects.Fig. 6 is the Raman collection of illustrative plates of the graphite/titanium oxide composite film with hollow nano tapered array structure after above-described embodiment 4 recombining process are processed surface of metal titanium.As shown in the figure, the peak shape of laminated film can be divided into two portions substantially, front four peaks overlap substantially with the peak value of anatase-type titanium oxide, and the peak that is in 1537 beam location is the characteristic peak of crystalline graphite, and the chemical constitution of laminated film contains titanium oxide and the crystalline graphite of Detitanium-ore-type as can be known.
Inject and the processing of deposition technique recombining process by anodizing technology of the present invention and plasma immersion ion, form in surface of metal titanium composite graphite/thin film of titanium oxide that one deck has hollow nano tapered array structure.Nanostructure has coniform sealing profile, the characteristic of inner hollow, and becoming to be grouped into is graphite and anatase-type titanium oxide nanocrystal and amorphous graphite.Therefore, adopt the method for preparing nano composite material based on surface of metal titanium of the present invention, will obtain a kind of novel graphite with hollow nano tapered array structure/titanium oxide composite film material.
Industrial applicability: the present invention processes through recombining process of the present invention in surface of metal titanium, can build hollow taper array nanostructure in surface of metal titanium, realize the preparation of graphite/titanium oxide composite nano materials, can be advantageously applied in nano material design and preparation.
Claims (12)
1. preparation method who prepares nano composite material based on surface of metal titanium, it is characterized in that, comprise that surface of metal titanium rule titania nanotube array film is carried out carbon plasma immersion ion injection technology makes carbon salty long-pending at nanotube, forms carbon containing titanium oxide nanotubes film with this; With the carbon containing titanium oxide nanotubes film that inject to process forms through the carbon plasma immersion ion is carried out carbon plasma immersion ion depositing treatment, form the graphite/titanium oxide composite film with hollow nano tapered array in surface of metal titanium with this.
2. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 1, is characterized in that, carry out that the carbon plasma immersion ion injects or during depositing treatment take high purity graphite as negative electrode.
3. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 1, it is characterized in that, carry out carbon plasma immersion ion depositing treatment to injecting through the carbon plasma immersion ion carbon containing titanium oxide nanotubes film of processing formation, making nanometer mouth of pipe carbon laydown is the ring-type rete.
4. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 3, is characterized in that, described ring-type rete forms for successively growth.
5. the described preparation method who prepares nano composite material based on surface of metal titanium of any one according to claim 1 to 4, is characterized in that, described plasma immersion ion injects treatment process condition and is: the base vacuum degree is 3.0 * 10
-3～5.0 * 10
-3Pa, injecting voltage are that 15～40kV, pulse-repetition are that 5～9Hz, pulsewidth are that 200～500 μ s, injection length are 30～120 minutes.
6. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 5, is characterized in that, described plasma immersion ion injects treatment process condition and is: the base vacuum degree is 4.0 * 10
-3Pa, injecting voltage are 20kV, and pulse-repetition is 8Hz, and pulsewidth is 450 μ s, and injection length is 60 minutes.
7. the described preparation method who prepares nano composite material based on surface of metal titanium of any one according to claim 1 to 4, is characterized in that, described plasma immersion ion depositing treatment processing condition: the base vacuum degree is 3.0 * 10
-3～5.0 * 10
-3Pa, pulsed voltage are that 200～600V, pulse-repetition are that 5～9Hz, pulsewidth are that 1000～4000 μ s, dutycycle are 10%～30%, depositing time is 30～120 minutes.
8. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 7, is characterized in that, described plasma immersion ion depositing treatment processing condition are: the base vacuum degree is 4.0 * 10
-3Pa, pulsed voltage is 450V, and pulse-repetition is 8Hz, and pulsewidth is 2000 μ s, and dutycycle is 15%, depositing time is 60 or 120 minutes.
9. the described preparation method who prepares nano composite material based on surface of metal titanium of any one according to claim 1-4, is characterized in that, by anodizing technology at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.
10. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 9, described oxidation voltage is 20～80V, oxidization time is 1～96 hour.
11. according to claim 1 to 10, the described method preparation of any one prepares nano composite material based on surface of metal titanium, it is characterized in that, described matrix material is the graphite/titanium oxide composite film of hollow nano tapered array, and described nanostructure has coniform sealing profile.
12. graphite/titanium oxide composite film according to claim 11 is characterized in that, it is graphite and anatase-type titanium oxide nanocrystal and amorphous graphite that the one-tenth of described graphite/titanium oxide composite film is grouped into.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210209846 CN102677055B (en) | 2012-06-25 | 2012-06-25 | Nano composite material based on titanium metal surface and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210209846 CN102677055B (en) | 2012-06-25 | 2012-06-25 | Nano composite material based on titanium metal surface and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102677055A CN102677055A (en) | 2012-09-19 |
| CN102677055B true CN102677055B (en) | 2013-11-06 |
Family
ID=46809587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210209846 Active CN102677055B (en) | 2012-06-25 | 2012-06-25 | Nano composite material based on titanium metal surface and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102677055B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105038903B (en) * | 2015-07-27 | 2018-04-03 | 江苏大学 | A kind of titanium alloy surface solid-state In-situ reaction antifriction antiwear material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8518420B2 (en) * | 2010-03-26 | 2013-08-27 | Board of Trustees of the Universtiy of Arkansas | Enhanced bone cells growth and proliferation on TiO2 nanotubular substrates treated by radio-frequency plasma discharge |
| CN102345135B (en) * | 2011-09-22 | 2013-05-15 | 中国人民解放军第四军医大学 | Preparation method for silver-carrying dental implant |
-
2012
- 2012-06-25 CN CN 201210209846 patent/CN102677055B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102677055A (en) | 2012-09-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Berger et al. | Self‐organized TiO2 nanotubes: Factors affecting their morphology and properties | |
| Wu et al. | Electrochemical synthesis and applications of oriented and hierarchically quasi-1D semiconducting nanostructures | |
| Mahadik et al. | Syntheses and electronic structure engineering of transition metal nitrides for supercapacitor applications | |
| Wang et al. | One-dimensional titania nanostructures: synthesis and applications in dye-sensitized solar cells | |
| Su et al. | Fast fabrication of Ta2O5 nanotube arrays and their conversion to Ta3N5 for efficient solar driven water splitting | |
| Wu et al. | Progress in the synthesis and applications of hierarchical flower-like TiO2 nanostructures | |
| Chen et al. | Fabrication and characterization of highly-ordered valve-metal oxide nanotubes and their derivative nanostructures | |
| Masuda et al. | Multineedle TiO2 nanostructures, self-assembled surface coatings, and their novel properties | |
| Sobaszek et al. | Fabrication and characterization of composite TiO2 nanotubes/boron-doped diamond electrodes towards enhanced supercapacitors | |
| Gao et al. | MnO2–TiO2/C nanocomposite arrays for high-performance supercapacitor electrodes | |
| Lai et al. | Fabrication of patterned CdS/TiO2 heterojunction by wettability template-assisted electrodeposition | |
| Kapusta-Kołodziej et al. | 3D nanoporous titania formed by anodization as a promising photoelectrode material | |
| KR20100075032A (en) | Manufacturing method of self-organized anodic titanium oxide nanotube arrays and control of the anodic titanium oxide nanotube thereby | |
| Burungale et al. | Studies on effect of temperature on synthesis of hierarchical TiO2 nanostructures by surfactant free single step hydrothermal route and its photoelectrochemical characterizations | |
| Li et al. | Fast fabrication of highly regular and ordered ZrO2 nanotubes | |
| Maile et al. | Facial growth of Co (OH) 2 nanoflakes on stainless steel for supercapacitors: effect of deposition potential | |
| Naveenraj et al. | Nanosized tantala based materials–synthesis and applications | |
| Ahila et al. | Influence of annealing on phase transformation and specific capacitance enhancement in Bi2O3 | |
| CN103225104A (en) | Single crystal anatase titanium dioxide nano-tube array and preparation method thereof | |
| Li et al. | A review on the low-dimensional and hybridized nanostructured diamond films | |
| Margaret et al. | A comparative study of nanostructures of CuO/Cu2O fabricated via potentiostatic and galvanostatic anodization | |
| Li et al. | Fabrication of highly ordered Ta2O5 and Ta3N5 nanorod arrays by nanoimprinting and through-mask anodization | |
| CN102677055B (en) | Nano composite material based on titanium metal surface and preparation method thereof | |
| Zhang et al. | Enlarged capacitance of TiO 2 nanotube array electrodes treated by water soaking | |
| KR101399391B1 (en) | Method of manufacturing titanium-niobium alloy nano structure |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |