CN102677055A - 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
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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, belong to nano material preparation and metal surface properties modification technical field in the surface of metal titanium preparation.
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, numerous areas such as environment protection obtain extensive studies and application.The titanium oxide nanotubes thin-film material had both had the functional of material itself; The tubulose geometry that has nanoscale again; Have the performance anisotropy simultaneously, prepare characteristics such as simple, make it as one type of new functional type nano film material in-depth with widen research and application in each field.
Anodizing technology is owing to low cost equipment, and advantages such as the technology of simple controllable are widely used in metal material surface and modify and modification.Zwilling (Surface and Interface Analysis 1999; 27 (7): 629-637.) wait the people to find that the anodic oxidation of titanium base material can generate the nanometer porous titanium oxide film in its surface in situ oxidation in the fluorine-containing electrolytic solution, make anodizing technology become the major technique means that generate the nano-titanium oxide thin-film material based on titanium substrate surface in-situ oxidation.Through 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&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 through extraneous bias voltage and realize high-octane ion implantationly, utilize to inject the generation that ionic diffusion and energy cohesion realize the compound and surface nano-structure of sample surfaces composition multielement easily.People such as Lifshitz research shows injects the forming core that is beneficial to nano surface crystal grain by high energy ion (Science 2002,297 (5586): 1531-1533.).With other process for modifying surface relatively, plasma immersion ion injects and has unique advantage: ion implantation process is the thermal nonequilibrium process, does not receive the restriction of metallurgy rule, can realize that most of ionic inject sample surfaces is carried out modification and modification; Simultaneously ion implantation process is instantaneous heat-processed, can the atarting material internal structure, the variation of composition and outer shape; In addition; The PIII&D technology has high reaction activity and omnibearing characteristics; Can be effectively carry out that uniform ion is injected and deposition, 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 " heterotypic material.
Yet the single The Nomenclature Composition and Structure of Complexes characteristic 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 nano-titanium oxide thin-film material composition and the structure that the surface of metal titanium in-situ oxidation generates in the prior art; How to realize the nanometer of material system, compoundization is to realize that its functionalization is the key issue in novel material design and the preparation.
Summary of the invention
The problems referred to above in the face of the prior art existence; The present invention is intended to through nanoscale special construction design on the implementation structure simultaneously and forms the recombining process of going up the nanocrystal Composite 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 present 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 injection of carbon plasma immersion ion and depositing treatment technology, forms the graphite/titanium oxide composite film with hollow nano tapered array in surface of metal titanium with this.
In the present invention, preferably carrying out that the carbon plasma immersion ion injects or be negative electrode during depositing treatment with the high purity graphite.With the carbon element source, find broad application by and characteristics that be easy to shape cheap because of it as experiment for graphite; High purity graphite has the high purity characteristics, after the pulse ionization, can form evenly high-density monovalence carbonium ion plasma body.This carbon plasma has simple behavioural characteristic and has the advantages that to control under magnetic field and effect of electric field, help the 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 30 ~ 120 minutes the processing condition, utilize said plasma immersion ion to inject treatment process and the regular titania nanotube array film on titanium metal top layer is got into carbon ion inject.Like this, can make carbon laydown, obtain carbonaceous titanium oxide nanotubes film at the nanometer mouth of pipe.
Said 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 30～120 minutes the processing condition.
To pass through plasma immersion ion injects carbon ion and handles carbon containing titanium oxide nanotubes film that surface of metal titanium obtains and carry out the plasma immersion ion depositing treatment and can make carbon laydown at nanotube interruption-forming ring-type rete.Again, said ring-type rete forms for successively generating.Because its special surface structure of titanium oxide nanotubes influences the formation of outer plasma sheath; Carbon ion receives 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 said carbon ion injects and carries out the carbon ion deposition on the regular titania nanotube array film, and regular titania nanotube array pattern is replaced by nanometer taper array of structures fully.Obtain graphite/titanium oxide composite film with hollow nano tapered array in surface of metal titanium formation.Surface of metal titanium is handled the titanium oxide nanotubes film that obtains through anodizing technology, and its surface presents ultra water-wet behavior; After carrying out carbon plasma injection or deposition technique processing,, can realize progressively that film surface is from ultra hydrophilic transformation to hydrophobic process according to the difference of degree of treatment.The characteristic of utilizing this hydrophilic and hydrophobic to change, laminated film can be applied to the automatically cleaning field; Graphite/titanium oxide is compound simultaneously can realize the photocatalysis of titania meterial in visible-range, in environment protection such as WWT and outdoor anti-pollution layer or film field, possibly obtain research and application.
Among the preparation method of the present invention, adopt anodizing technology at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.This method is the effective way that obtains independent nano-pipe array thin film, and the Ti sheet that breaks away from behind the array can directly be utilized once more.In addition, preferably, said oxidation voltage is 30～80V, and oxidization time is 5～15 hours.Can on the titanium metal base, make complete, independent, orderly nano-pipe array thin film better like this, and geomery is controlled.
The present invention carries out the carbon plasma immersion ion through the regular titania nanotube array film to surface of metal titanium and injects processing and depositing treatment; Can form graphite/titanium oxide composite film in surface of metal titanium with hollow nano tapered array structure; Its constitutional features is a nanometer taper array; Its surface presents hydrophobic property, and the carbon plasma technical finesse realizes that the film surface hydrophilic and hydrophobic changes; Combines simultaneously to constitute to seal hollow structure, possibly be applied to the loading of medicine and transport with nano-tube array.Said graphite/titanium oxide composite film the component that preferably forms is the TiOx nano crystal grain and the amorphous graphite of graphite and Detitanium-ore-type; Crystalline graphite/titanium oxide composite film can effectively reduce the energy gap of titanium oxide; Be implemented in the photocatalysis of visible-range, be applied in photochemical catalysis and environmental pollution improvement field.
The present invention realizes the preparation of graphite/titanium oxide composite nano materials, solves nano-titanium oxide thin-film material composition and the structure that the surface of metal titanium in-situ oxidation generates in the prior art 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 anodize 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 handling, 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 laminated 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 handled, and interior illustration is the high power shape appearance figure;
Fig. 3 illustrates through recombining process of the present invention and handles the side shape appearance figure with hollow nano tapered array structure laminated film that obtains after the surface of metal titanium;
Fig. 4 illustrates through recombining process of the present invention and handles the cross section transmission electron micrograph with hollow nano tapered array structure laminated film that obtains after the surface of metal titanium, and interior illustration sheet is electron diffraction pattern (left side down) and regional area high magnification map sheet (upper right);
Fig. 5 a illustrates high resolution photoelectron spectrum (XPS) figure with hollow nano pyramidal structure laminated film surface titanium elements that after recombining process of the present invention is handled surface of metal titanium, obtains;
Fig. 5 b illustrates high resolution photoelectron spectrum (XPS) figure with hollow nano pyramidal structure laminated film surface carbon element that after recombining process of the present invention is handled surface of metal titanium, obtains;
Fig. 6 illustrates the Raman collection of illustrative plates with hollow nano pyramidal structure laminated film surface that after recombining process of the present invention is handled surface of metal titanium, obtains.
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 combine following embodiment to further specify the present invention, should be understood that following embodiment only is used to explain 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 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 terepthaloyl moietie mixing solutions, and oxidation voltage is 20 ~ 80V, and oxidization time is 1 ~ 96h.Preferred processing condition and parameter are: electrolytic solution is the terepthaloyl moietie 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 injection and deposition technique to carry out carbon ion injection or deposition on above-mentioned regular titania nanotube array film surface, preferably be negative electrode with the high purity graphite.
Processing parameter when carrying out the carbon ion injection 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 sedimentary processing parameter of carbon ion 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 handled, the surface of metal titanium original position generated the graphite/titanium oxide composite film with hollow nano tapered array structure, and its three-dimensional structure is the coniform cap of titanium oxide nanotubes matrix bond graphite, formed the nano-array of hollow; Component is graphite and the 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 a nanometer taper array, combines to constitute the sealing hollow structure with nano-tube array, and component is the TiOx nano crystal grain and the amorphous graphite of graphite and Detitanium-ore-type.Recombining process of the present invention nanoscale special construction design and form and go up the nanocrystal Composite Preparation on the implementation structure simultaneously.
Embodiment further give an example below to specify exemplary process of the present invention.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 through buying.The experimental technique of unreceipted actual conditions in the following example usually according to normal condition, for example is " 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.Only if definition or explanation are arranged in addition, the same meaning that all specialties used herein and scientific words and those skilled in the art are familiar with.Any in addition with the similar content of putting down in writing or the method that is equal to and material all can be applicable in the inventive method.Other aspects of the present invention are because the disclosure of this paper is to understand easily to those skilled in the art.
(1) after the pure titanium metal sheet process polished finish with 10mm * 10mm * 1mm, uses acetone, alcohol and deionized water ultrasonic cleaning clean successively, each 15 minutes, obtain clean surface (seeing shown in Figure 1) uniformly.Adopt anodizing technology, at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.Concrete processing condition and parameter are seen shown in the table 1.The surface topography map that under this processing parameter, obtains sees that shown in Fig. 2 a, the result shows the nano-tube array structure of surface of metal titanium formation rule;
Table 1 anode oxidation process condition and parameter
(2) to after handling 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; With the high purity graphite is negative electrode; Regular titania nanotube array film to surface of metal titanium carries out the carbon ion injection, obtains carbonaceous titanium oxide nanotubes film.Concrete injection parameter is seen shown in the table 2; The surface topography map that under this injection parameter, obtains sees shown in Fig. 2 b that the result shows that the tube wall at nanometer mouth of pipe place thickens, and shows that having carbon to be fond of salty food at nanotube amasss:
Table 2 carbon ion injection parameter
(3) inject carbon ion through anodizing technology and plasma immersion ion and handle the carbon containing titanium oxide nanotubes film that surface of metal titanium obtains and carry out the plasma immersion ion depositing treatment above-mentioned.Concrete carbon ion deposition parameter is seen shown in the table 3.The surface topography map that under this deposition parameter, obtains is seen shown in Fig. 2 c; Find the titanium oxide nanotubes surface topography generation considerable change afterwards of carbon ion deposition through 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 vestige of growth is successively arranged clearly;
Table 3 carbon ion deposition parameter
Present embodiment step (1) and (2) are same as embodiment 1, are omitting its detailed description.(3) will inject carbon ion through the foregoing description 1 anodizing technology and plasma immersion ion handles the carbon containing titanium oxide nanotubes film that surface of metal titanium obtains and carries out the plasma immersion ion depositing treatment.Concrete carbon ion deposition parameter is seen shown in the table 4; The surface topography map that under this deposition parameter, obtains sees shown in Fig. 2 d that the 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 constitutes enclosed construction, but can find out that from the damaged position of part nanometer taper cap in top keeps hollow structure, and is as shown in Figure 3.Do cross section transmission electron microscopy sign to having hollow nano tapered array structure laminated 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 tangible carbon laydown film successively to grow and stay has a large amount of particles to occur at its combining site, shows it is the nanocrystal of graphite and titanium oxide through choosing electron diffraction and high magnification amplification picture:
Table 4 carbon ion deposition parameter
The graphite/titanium oxide composite film with hollow nano tapered array structure that will after the foregoing description 2 anodizing technologies and plasma immersion ion injection and deposition technique recombining process processing surface of metal titanium, obtain carries out the surface light electronic spectrum 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 the foregoing description 4 recombining process are handled surface of metal titanium, and Fig. 5 b is the high resolution XPS collection of illustrative plates of the graphite with the hollow nano tapered array structure/titanium oxide composite film surface carbon element after the foregoing description 4 recombining process are handled surface of metal titanium.In scheming, can know that surperficial titanium elements mainly exists with the form of titanium oxide, and carbon exists crystalline graphite and two kinds of forms of non-crystalline graphite to exist.
The graphite/titanium oxide composite film with hollow nano tapered array structure that will after the foregoing description 2 anodizing technologies and plasma immersion ion injection and deposition technique recombining process processing surface of metal titanium, obtain carries out surperficial Raman spectrum 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 the foregoing description 4 recombining process are handled surface of metal titanium.As shown in the figure; The peak shape of laminated film can be divided into two portions basically; Preceding four peaks overlap with the peak value of anatase-type titanium oxide basically, and the peak that is in 1537 beam location then is the characteristic peak of crystalline graphite, can know that the chemical constitution of laminated film contains the titanium oxide and the crystalline graphite of Detitanium-ore-type.
Inject and the processing of deposition technique recombining process through anodizing technology of the present invention and plasma immersion ion, form composite graphite/thin film of titanium oxide that one deck has hollow nano tapered array structure in surface of metal titanium.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 of the present inventionly to prepare the method for nano composite material, will obtain a kind of novel graphite with hollow nano tapered array structure/titanium oxide composite film material based on surface of metal titanium.
Industrial applicability: the present invention handles through recombining process of the present invention in surface of metal titanium; Can make up 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 the preparation.
Claims (13)
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 the carbon plasma immersion ion to be injected and depositing treatment, forms the graphite/titanium oxide composite film with hollow nano tapered array with this in surface of metal titanium.
2. according to claim 1ly prepare the preparation method of nano composite material, it is characterized in that, carrying out that the carbon plasma immersion ion injects or be negative electrode during depositing treatment with the high purity graphite based on surface of metal titanium.
3. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 2; It is characterized in that; The regular titania nanotube array film of surface of metal titanium is carried out carbon plasma immersion ion injection technology make carbon salty long-pending, form carbon containing titanium oxide nanotubes film with this at nanotube.
4. the preparation method who prepares nano composite material based on surface of metal titanium according to claim 3; It is characterized in that; Carry out carbon plasma immersion ion depositing treatment to injecting the carbon containing titanium oxide nanotubes film of handling formation through the carbon plasma immersion ion, making nanometer mouth of pipe carbon laydown is the ring-type rete.
5. according to claim 4ly prepare the preparation method of nano composite material, it is characterized in that said ring-type rete is that successively growth forms based on surface of metal titanium.
6. according to each describedly prepares the preparation method of nano composite material based on surface of metal titanium in the claim 1 to 5, it is characterized in that said 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.
7. according to claim 7ly prepare the preparation method of nano composite material, it is characterized in that said plasma immersion ion injects treatment process condition and is: the base vacuum degree is 4.0 * 10 based on surface of metal titanium
-3Pa, injecting voltage are 20kV, and pulse-repetition is 8Hz, and pulsewidth is 450 μ s, and injection length is 60 minutes.
8. according to each describedly prepares the preparation method of nano composite material based on surface of metal titanium in the claim 1 to 7, it is characterized in that said 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.
9. according to claim 8ly prepare the preparation method of nano composite material, it is characterized in that said plasma immersion ion depositing treatment processing condition are: the base vacuum degree is 4.0 * 10 based on surface of metal titanium
-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.
10. according to each describedly prepares the preparation method of nano composite material based on surface of metal titanium among the claim 1-9, it is characterized in that, through anodizing technology at surface of metal titanium in-situ oxidation create-rule titania nanotube array film.
11. according to claim 10ly prepare the preparation method of nano composite material based on surface of metal titanium, said oxidation voltage is 20～80V, oxidization time is 1～96 hour.
12. one kind prepares nano composite material according to each described method preparation in the claim 1 to 11 based on surface of metal titanium; It is characterized in that; Said matrix material is the graphite/titanium oxide composite film of hollow nano tapered array, and said nanostructure has coniform sealing profile.
13. graphite/titanium oxide composite film according to claim 12 is characterized in that, it is graphite and anatase-type titanium oxide nanocrystal and amorphous graphite that the one-tenth of said graphite/titanium oxide composite film is grouped into.
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| US20110236435A1 (en) * | 2010-03-26 | 2011-09-29 | Board Of Trustees Of The University Of Arkansas | ENHANCED BONE CELLS GROWTH AND PROLIFERATION ON TiO2 NANOTUBULAR SUBSTRATES TREATED BY RADIO-FREQUENCY PLASMA DISCHARGE |
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| CN105038903A (en) * | 2015-07-27 | 2015-11-11 | 江苏大学 | Titanium alloy surface solid in-situ composite friction-reducing and wear-resisting material |
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