CN108070860A - Surface modifying method of a kind of titanium-based and tantalum metal alkyl materials and products thereof and purposes - Google Patents
Surface modifying method of a kind of titanium-based and tantalum metal alkyl materials and products thereof and purposes Download PDFInfo
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- CN108070860A CN108070860A CN201711372004.2A CN201711372004A CN108070860A CN 108070860 A CN108070860 A CN 108070860A CN 201711372004 A CN201711372004 A CN 201711372004A CN 108070860 A CN108070860 A CN 108070860A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/12—Gaseous compositions
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
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Abstract
The present invention relates to surface modifying method of a kind of titanium-based and tantalum metal alkyl materials and products thereof and purposes, the surface modifying method includes the following steps：(1) pre-process：Titanium-based or tantalum metal alkyl materials are polished to bright luster；(2) photoetching：Surface after step (1) is polished coats photoresist layer, and after curing, exposure carries out photoetching, development；(3) ICP or RIE etchings：Matrix after step (2) is developed is put into ICP or RIE intracavitary, is performed etching with etching gas, removes the photoresist layer, and obtaining surface has the medical metal material of nanotopology.Topology is controllable, and method is easy to operate, without SiO2Or metal does surface protection, can design different surface topography guiding cell growths as needed, increase adherence rate；It has a good application prospect.
Description
Technical field
The present invention relates to medical metal material process for modifying surface field more particularly to a kind of titanium-based and tantalum metal alkyl materials
Surface modifying method and products thereof and purposes.
Background technology
Titanium or titanium alloy material, which has become the implantation such as orthopaedics, gear division and angiocarpy or instrument main raw material(s), tantalum, to be had
Great friction coefficient, this will be able to have preferable mechanical stability and when tantalum is implanted into animal body without surrounding inflammation instead
With excellent biocompatibility, therefore important function is played in the surgical operations such as Fracture internal fixaiion.Generally believe implant
Material surface and interaction of the surrounding tissue on molecule and cellular level, cell and protein size are 1~100 respectively
μm and 1~10nm, therefore, biomaterial surface microstructure has an important influence on the adherency of cell, multiplication and differentiation etc..
In view of nature bone is mainly made of the hydroxyapatite (HA) with micro nano structure, for orthopaedics and dental material
For, roughness of the design with micro-nano-scale is most important to improving tissue integration.The study found that with topological structure
Rough surface to the flatter surface-sensitive degree of the Proliferation, Differentiation of osteoblast enhance.For its table after material surface micro-nanoization
Face structure is conducive to the characteristics of adherency, differentiation and multiplication of internal cell, and mesh first three can realize that metal material surface is micro-nano
The common method of change：(1) face coat：Particle with nanoscale is fixed on material surface, is formed and forms phase with substrate
Same or different nanostructured surface laye；(2) itself micro-nanoization of surface：Being adopted as non-equilibrium processing method for polycrystalline material can
Increase material surface roughness and free energy, original open grain structure is made gradually to be refined to micro-nano magnitude, mainly there is surface at present
The methods of machining processes, micro-arc oxidation (MAO) and laser surface processing；(3) hybrid mode：By nano surface skill
Art is organically combined with chemical treatment, i.e., forms the micro nanocrystalline solid solution different from matrix composition in the nanostructured surface laye of material
Or compound.
CN102586786A discloses a kind of method that titanium surface forms graded multi-hole shape, clear including the polishing of titanium sample
- bead-acid etching-anodic oxidation-ultrasonic cleaning is washed, biologically active classifying porous shape is formed on pure titanium surface
Looks, and with the ionic compound TiO of the thicker high biochemistry stability combined by ionic bond2Layer.CN102921037A
A kind of method that titanium implant surface prepares multistage micrometer structure is disclosed, titanium is polished, oil removal treatment cleaning, then hydrofluoric acid,
Nitric acid, mixed solution of hydrogen peroxide acid etching cleaning, then carry out blasting treatment, by the titanium after blasting treatment be placed in pickling solution into
One step acid etching, then it is thermally treated resulting in the titanium implant on multistage micrometer structure surface.CN103981523A discloses a kind of super
Hydrophily Ti6Ai7Ni surface sand-blasting acid etching methods, by Ti6Ai7Ni is pre-processed, sandblasting, acid etching, cleaning table
Surface treatment process, prepares micron order rough porous titanium alloy surface, and surface possesses superpower hydrophily.
CN105925949A discloses the preparation method of a kind of titanium or titanium alloy surface micro-nano porous structure, comprises the following steps：Titanium
Or the surface cleaning processing of titanium alloy；One layer of copper coating of electroplating surface or magnetron sputtering of titanium or titanium alloy；Heat treatment is former by copper
Son diffuses into the surface of titanium or titanium alloy；Alloy treatment is taken off using solid phase method magnesium powder or liquid phase method molten state magnesium；Finally use
Acid and water cleaning and drying；Obtain surface micronano porous titanium or titanium alloy.
The technologies such as anodic oxidation, differential arc oxidation and laser treatment need special installation, and operating process is complex, and by
Using more chemical reagent in preparation process, easily residue in final products, therefore, such technology is not being faced also at present
It is used on bed.In contrast, chemical method has many advantages, such as simple, easy to operate and at low cost, in dentistry implant
It is commercialized in terms of the modification of surface.However, major part chemical treatment method all refers to strong acid and strong base at present, in order to avoid
Residual acid-base pair cell and tissue damage, and planting body prepared by chemical method is required for, by eluting for a long time, treating
Journey is cumbersome, low production efficiency, be easy to cause hydrogen embrittlement, and processing cost is higher.In addition, such method is generally better at regulation and control micron level
Pattern, it is extremely limited to nanostructured ability of regulation and control.
CN106498397A discloses a kind of topological in titanium-based implant surface in-situ construction multi-stage nano based on salt erosion
The method of structure.Not only to pass through prolonged elution, and the regular texture that can be designed cannot be formed, using limited.
The majority of medical metal material surface micronanoization research at present has concentrated on table caused by the machining processes of surface
Face micro-nanoization, main method include mechanical lapping, ultrasonic shot peening, high speed impact, micro-arc oxidation etc..It but cannot be controllably
Change surface texture or the diversified surface microscopic topological structure of designed, designed.And laser processing of materials surface is used, laser
The energy of generation makes material surface melting than more serious, it is difficult to maintain the figure of regularization and due to the limit of laser beam size
System, graphics resolution be not high, it is impossible to reach the pattern requirement of submicron-scale, it is impossible to while realize that large-scale surface patterns.
Therefore need to develop the medical metal materials surface modifying methods such as a kind of effective titanium or titanium alloy, tantalum and tantalum alloy, Ke Yike
Control ground changes surface texture or the diversified surface microscopic topological structure of designed, designed.
The content of the invention
In view of problems of the prior art, one of the objects of the present invention is to provide a kind of effective titaniums and titanium to close
The medical metal materials surface modifying methods such as gold, tantalum and tantalum alloy, can controllably change surface texture or designed, designed is more
The surface microscopic topological structure of sample.The configuration of surface being modified is controllable, easy to operate, is imparted after material surface micro-nanoization
Its new surface texture and state, the advantages of making it have nanobiology.With excellent biocompatibility and cell
The advantages that adherent rate is high, multiplication is fast.
In order to achieve this, the present invention uses following technical scheme：
In a first aspect, the surface modifying method of a kind of titanium-based of present invention offer and tantalum metal alkyl materials, described " and " represent
The meaning of "or", the surface modifying method both can be used for titanium-based metal material, can be used for tantalum metal alkyl materials, including
Following steps：
(1) pre-process：Titanium-based or tantalum metal alkyl materials are polished to bright luster；
(2) photoetching：Surface after step (1) is polished coats photoresist layer, and after curing, exposure carries out photoetching, development；
(3) ICP is etched：Matrix after step (2) is developed is put into ICP or deep reaction ion etching (RIE) intracavitary, with quarter
Erosion gas performs etching, and removes the photoresist layer, and obtaining surface has the medical metal material of nanotopology.
The method of the invention is a kind of new medical metal material surface modifying method, for the first time by photoetching and inductance coupling
It closes plasma (ICP) etching or deep reaction ion etching (RIE) combines, it, need not applied to titanium-based or tantalum metal alkyl materials
SiO2Or the pattern of design is retained in titanium and tantalum-based materials by splash-proofing sputtering metal as protective layer by gluing, exposure, development step
Surface etches using ICP and etches exposure area, leaves non-exposed areas, finally remove to obtain by non-exposed area photoresist
There is the surface of topology, the method controllably large area can change medical metal material surface microstructure；Material surface
Can be with designed, designed figure of different shapes, such as can be the arbitrary graphics such as groove, cylinder, cell is in inside grooves and outside
Fit closely material walls elongation growth.Material surface is combined surface microstructure by photoetching and ICP lithographic techniques and changes
Become, obtaining surface has the medical metal material of the controllable micron-nano topological structure of rule.ICP etchings are general in the prior art uses
In semi-conducting materials such as etching silicon wafers, the process applied to the surface treatment of this field medical metal material has not been reported.
In the present invention, micron-nano topological structure can effectively guide Oesteoblast growth, increase osteoblast adherency, add
The differentiation of fast cell；Pattern also can designed, designed, such as groove, cylinder, size can be with designed, designeds from nanoscale to micron
Scale, such as can be 0.5 μm, 1 μm, 3 μm, 5 μm, 100 μm, as space is limited and for it is concise the considerations of, the present invention is no longer poor
Specific pattern, pattern and size that the scope includes are enumerated to the greatest extent.Correspondingly, the depth of figure can be controlled voluntarily, example
It such as can be 100nm, 200nm, 800nm, 1800nm, can adjust different ICP or RIE etch periods and change graphics depth.It is described
The pattern of material surface topological structure can designed, designed, line thickness can change from nanometer to micron, such as 0.5 μm, 1 μm, 3 μ
M, 5 μm, 100 μm, as space is limited and for it is concise the considerations of, the present invention no longer scope described in exclusive list include it is specific
Value.
Preferably, the titanium-based metal material includes titanium or titanium alloy, such as Ti6Al4V etc.；The tantalum metal alkyl materials bag
Include tantalum or tantalum alloy, as space is limited and for it is concise the considerations of, the present invention all materials that no longer scope described in exclusive list includes
Material.
Preferably, step (1) polishing includes mechanical polishing and/or vibropolish.
Preferably, it is described mechanical polishing include with sand paper rubbing down close/or with polish cloth polishing.
Preferably, shot-peening and/or Ion Cleaning are further included after the polishing.
Preferably, the thickness of step (2) described photoresist layer be 0.5~5 μm, such as 0.5 μm, 0.8 μm, 1 μm, 1.5 μm,
2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm etc., preferably 2.5~3.5 μm.
Preferably, step (2) curing includes drying.
Preferably, the time of the drying be 1~10min, such as 1min, 2min, 3min, 4min, 5min, 6min,
7min, 8min, 9min or 10min etc., preferably 3~4min.
Preferably, step (2) exposure includes the exposure of UV contact formula.
The time deficiency of photolithographic exposure cannot then highlight the surface microstructure of design completely, and photoetching overlong time will be easy
It caused to show, three-dimensional microstructures cannot be completely etched in etching process, it is preferable that the time of step (2) described exposure
For 1~15s, such as 1s, 2s, 3s, 4s, 5s, 6s, 7s, 8s, 9s, 10s, 11s, 12s, 13s, 14s or 15s etc., preferably 6.0~
7.5s。
Preferably, the time of step (2) described development be 5~120s, such as 5s, 10s, 20s, 30s, 50s, 60s, 80s,
100s, 110s or 120s etc., preferably 20~50s.
Preferably, further included after step (2) described development：Drying.
Preferably, step (3) described etching gas include chloride and/or fluoro-gas.
Preferably, the chlorine-containing gas includes Cl2And/or BCl3。
Preferably, the fluoro-gas includes CF4。
Preferably, the etching gas further include inert gas.
Preferably, group of the inert gas including any one in argon gas, nitrogen, helium or neon or at least two
It closes；
Preferably, step (3) described etching gas are argon gas, Cl2And BCl3Mixed gas.
Preferably, the flow of the argon gas is 0~90SCCM, the Cl2Flow be 0~100SCCM, the BCl3's
Flow is 0~100SCCM, the Cl2Flow and the BCl3Flow difference when be 0.Certain etch rate is controlled to increase
The integrality of surface texture.
Preferably, the time of step (3) described etching be 1~30min, such as 1min, 2min, 5min, 10min,
15min, 20min, 25min or 30min etc., preferably 5~15min.
ICP etch periods are related with the depth that material and needs etch, and when material is pure titanium, select Ar, Cl2And CHCl3
Can be reached by mixing etching gas, etching 10min or so etching depth by 1.8 μm；When material closes for corrosion resistance titanium alloy or tantalum
Jin Shi can slow down titanium or tantalum and directly be reacted with gas, make material etch rate reduction, and etching depth also can accordingly become smaller.
As currently preferred technical solution, the surface modifying method of the titanium-based and tantalum metal alkyl materials is including as follows
Step：
(1) pre-process：Titanium-based or tantalum metal alkyl materials are through mechanical polishing, vibropolish, shot-peening, Ion Cleaning, until having
Bright luster；
(2) photoetching：The photoresist layer that surface coating thickness after step (1) is polished is 0.5~5 μm, front baking 1~
10min, photoresist layer cure, and UV contact formula exposes 1~15s and carries out photoetching, and develop 5~120s, rear to dry；
(3) ICP or RIE etchings：Matrix after step (2) is developed is put into ICP or RIE cavitys, with chlorine-containing gas and
Optional inert gas etches 1~60min, removes the photoresist layer, and obtaining surface has the medical gold of nanotopology
Belong to material.
Second aspect, the present invention, which provides a kind of surface, has the medical metal material of nanotopology, passes through such as first
The surface modifying method of the aspect titanium-based and tantalum metal alkyl materials is prepared.
The third aspect, the present invention provides medical metal material of the surface with nanotopology as described in second aspect
Purposes, the medical metal material that the surface has nanotopology are used for orthopaedics implant, tooth-implanting and angiocarpy bracket.
Compared with prior art, the present invention at least has the advantages that：
1. material surface topology prepared by the present invention is controllable, method is easy to operate, without SiO2Or metal does surface
Protection can design different surface topography guiding cell growths, increase adherence rate as needed.It is a kind of novel titanium-based
Or tantalum base table surface modification process, it has a good application prospect；
2. the present invention overcomes current mechanical processing and the low inferior position of resolution ratio of laser surface modification, traditional metal materials
Expect the uncontrollable problem of surface modifying method, the present invention is using photoetching combination ICP or RIE lithographic method, directly in titanium-based and tantalum
Primary surface controllably prepares the topology of different micro-nano-scales, can be also used in combination with the micro- sodium rice chemical industry skill of other surfaces,
With good processing compatibility.
Description of the drawings
Fig. 1 is titanium surface topology topography scan electron microscope prepared by the embodiment of the present invention 1；
Fig. 2 is Ti prepared by the embodiment of the present invention 96Al4The topology scanning electron microscope (SEM) photograph of V；
Fig. 3 is the scanning electron microscope (SEM) photograph for the topology that cell is prepared in the embodiment of the present invention 1；
Fig. 4 is scanning electron microscope (SEM) photograph of the cell on the flat titanium surface that comparative example 1 of the present invention is not surface-treated；
Fig. 5 is titanium surface topology topography scan electron microscope prepared by the embodiment of the present invention 11
Specific embodiment
Technical solution to further illustrate the present invention below with reference to the accompanying drawings and specific embodiments.But following reality
The simple example that example is only the present invention is applied, does not represent or limit the scope of the present invention, protection model of the invention
It encloses and is subject to claims.
Embodiment 1
A kind of surface modifying method of titanium metal material, step are as follows：
(1) pure titanium is selected as base material, respectively by the polishing of 180,360,1200 mesh sand paper, less than 1 μm polishing cloth
After vibropolish, the surface of bright luster is obtained；
(2) titanium sheet for the polishing for obtaining step (1), 3 μm of ZJ-304 thickness glue of spin coating, front baking 1min, UV contact formula
7.0s is exposed, develop 30s, dries 1min afterwards, etches 10min by ICP, acetone ultrasound washes off what is designed after photomask surface glue
Topology.
As shown in Figure 1, groove of the topology surface for 5 μm of width of design, atomic force microscope (AFM) test shows material
The depth that is etched is 1.8 μm.Titanium surface topology appearance and size manufactured in the present embodiment is uniform, and figure keeps very complete.
Embodiment 2
With differing only in for embodiment 1：Using 10 μm of line width mask plates.
Surface line width is obtained as 10 μm of complete topologies of groove structure.Illustrate that the present invention can be with the micro- sodium rice of other surfaces
Chemical industry skill is used in combination, and has good processing compatibility.
Embodiment 3
A kind of surface modifying method of titanium metal material, step are as follows：
(1) with embodiment 1；
(2) titanium sheet for the polishing for obtaining step (1), 4 μ m-thick ZJ-304 thickness glue of spin coating, front baking 1min, UV contact
Formula exposes 7.5s, and develop 50s, dries 1min afterwards, etches 15min by ICP, acetone ultrasound is designed after washing off photomask surface glue
Topology.
Titanium surface manufactured in the present embodiment with topology, the topology surface are to design 5 μm of width, deeply 2.4 μm
Groove, figure keep very complete.
Embodiment 4
A kind of surface modifying method of titanium metal material, step are as follows：
(1) with embodiment 1；
(2) titanium sheet for the polishing for obtaining step (1), 3 μ m-thick ZJ-304 thickness glue of spin coating, the exposure of UV contact formula
After 7.0s, the 30s that develops, 15min is etched by ICP, acetone ultrasound washes off the topology designed after photomask surface glue；
Titanium surface manufactured in the present embodiment with topology, the topology surface are to design 5 μm of width, deeply 2.4 μm
Groove, figure keep very complete.
Embodiment 5
A kind of surface modifying method of titanium metal material, step are as follows：
(1) with embodiment 1；
(2) titanium sheet for the polishing for obtaining step (1), 5 μ m-thick ZJ-304 thickness glue of spin coating, front baking 15min, UV contact
Formula exposes 15s, develops after 120s, dries 15min afterwards, etches 30min by ICP, acetone ultrasound obtains after washing off photomask surface glue
The topology of design.
Titanium surface manufactured in the present embodiment with topology, the topology surface are to design 5 μm of width, deeply 2.6 μm
Groove, figure keep very complete.
Embodiment 6
A kind of surface modifying method of titanium metal material, step are as follows：
(1) with embodiment 1；
(2) titanium sheet for the polishing for obtaining step (1), 0.5 μ m-thick ZJ-304 thickness glue of spin coating, front baking 1min, ultraviolet light connect
Touch exposes 2s, develops after 5s, dries 1min afterwards, etches 2min by ICP, acetone ultrasound is designed after washing off photomask surface glue
Topology.
Titanium surface manufactured in the present embodiment with topology, the topology surface are to design 5 μm of width, deeply 0.2 μm
Groove, figure keep very complete.
Embodiment 7
A kind of surface modifying method of titanium metal material, step are as follows：
(1) with embodiment 1；
(2) titanium sheet for the polishing for obtaining step (1), 0.2 μ m-thick ZJ-304 thickness glue of spin coating, front baking 1min, ultraviolet light connect
Touch exposes 7.0s, develops after 30s, 1min is dried afterwards, using RIE reactors and CF4, Ar mixed gas, gas flow rate is
10SCCM, etching duration 10min, acetone ultrasound wash off the topology designed after photomask surface glue.
The present embodiment titanium surface manufactured in the present embodiment with topology, the topology surface are 5 μm of width of design, deeply
0.8 μm of groove, figure keep very complete.
Embodiment 8
A kind of surface modifying method of tantalum metal alkyl materials, step are as follows：
(1) tantalum piece is taken, is successively polished by 180,360 and 1200 mesh sand paper, after polishing；
(2) with embodiment 1.
The present embodiment tantalum surface manufactured in the present embodiment with topology, the topology surface are 5 μm of width of design, deeply
1.2 μm of groove, figure keep very complete.
Embodiment 9
A kind of Ti6Al4The surface modifying method of V materials, step are as follows：
(1) Ti is selected6Al4V is polished by 180,360,1200 mesh sand paper as basis material, less than 1 μm of polishing cloth and
After vibropolish, the surface of bright luster is obtained；
(2) titanium sheet for the polishing for obtaining step (1), 3 μ m-thick ZJ-304 thickness glue of spin coating, front baking 1min expose 7.0s, show
Shadow 25s, dries 1min afterwards, etches 5min by ICP, acetone ultrasound washes off the topology designed after photomask surface glue.
Atomic force microscope (AFM) test shows that etching depth for 200nm, can equally obtain complete surface topography, such as
Shown in Fig. 2.
Embodiment 10
A kind of surface modifying method of tantalum-niobium alloy material, step are as follows：
(1) Ti is selected6Al4It as basis material, polishes by 180,360,1200 mesh sand paper, less than 1 μm of polishing cloth and shakes
After dynamic polishing, the surface of bright luster is obtained；
(2) titanium sheet for the polishing for obtaining step (1), 3 μ m-thick ZJ-304 thickness glue of spin coating, front baking 1min expose 7.0s, show
Shadow 25s, dries 1min afterwards, etches 5min by ICP, acetone ultrasound washes off the topology designed after photomask surface glue.
Atomic force microscope (AFM) test shows that etching depth for 0.6 μm, can equally obtain complete surface topography,
Embodiment 11
With embodiment 2 difference lies in：Mask plate is external 10 μ m, 10 μm of squares, intermediate 5 μm of circles of φ.
It obtains can be the topology that depth is 500nm structural integrities, as shown in Figure 5.
Comparative example 1
With differing only in for embodiment 1：Omit the processing step of step (2).
Cell tests：
Topological surfacing prepared by the embodiment of the present invention 1 and the flat titanium surface of 1 untreated material of comparative example are distinguished
Cell tests are carried out, test result is distinguished shown in Fig. 3, Fig. 4.It is compared with flat titanium surface, it can be seen that prepared by embodiment 1 opens up
It flutters on surfacing, cell is grown on topology surface along surface topography, more preferable in topological face side wall and surface fitting,
There is apparent feeler, cell is combined with basis material, can be with induced cell growth.And cell is flatly spread out on flat surfaces, is not had
There is apparent feeler to generate, it is impossible to closely be combined with matrix.It can be seen that topology and untreated material prepared by the present invention
Flat surfaces are compared to obviously with superior biocompatibility and adherence rate and multiplication rate.
Applicant states that the present invention illustrates the detailed process equipment of the present invention and technological process by above-described embodiment,
But the invention is not limited in above-mentioned detailed process equipment and technological processes, that is, it is above-mentioned detailed not mean that the present invention has to rely on
Process equipment and technological process could be implemented.Person of ordinary skill in the field it will be clearly understood that any improvement in the present invention,
The addition of equivalence replacement and auxiliary element to each raw material of product of the present invention, selection of concrete mode etc. all fall within the present invention's
Within protection domain and the open scope.
Claims (10)
1. the surface modifying method of a kind of titanium-based and tantalum metal alkyl materials, which is characterized in that include the following steps：
(1) pre-process：Titanium-based or tantalum metal alkyl materials are polished to bright luster；
(2) photoetching：Surface after step (1) is polished coats photoresist layer, and after curing, exposure carries out photoetching, development；
(3) ICP is etched：Matrix after step (2) is developed is put into ICP or RIE intracavitary, is performed etching with etching gas, removes
The photoresist layer, obtaining surface has the medical metal material of nanotopology.
2. the surface modifying method of titanium-based as described in claim 1 and tantalum metal alkyl materials, which is characterized in that the titanium-based gold
Belonging to material includes titanium or titanium alloy；The tantalum metal alkyl materials include tantalum or tantalum alloy.
3. the surface modifying method of titanium-based as claimed in claim 1 or 2 and tantalum metal alkyl materials, which is characterized in that step (1)
The polishing includes mechanical polishing and/or vibropolish；
Preferably, it is described mechanical polishing include with sand paper rubbing down close/or with polish cloth polishing；
Preferably, shot-peening and/or Ion Cleaning are further included after the polishing.
4. such as claims 1 to 3 any one of them titanium-based and the surface modifying method of tantalum metal alkyl materials, which is characterized in that
The thickness of step (2) described photoresist layer is 0.5~5 μm, preferably 2.5~3.5 μm；
Preferably, step (2) curing includes drying；
Preferably, the time of the drying is 1~10min, preferably 3~4min.
5. such as Claims 1 to 4 any one of them titanium-based and the surface modifying method of tantalum metal alkyl materials, which is characterized in that
Step (2) exposure includes the exposure of UV contact formula；
Preferably, the time of step (2) described exposure is 1~15s, preferably 6.0~7.5s.
6. such as Claims 1 to 5 any one of them titanium-based and the surface modifying method of tantalum metal alkyl materials, which is characterized in that
The time of step (2) described development is 5~120s, preferably 20~50s.
7. such as claim 1~6 any one of them titanium-based and the surface modifying method of tantalum metal alkyl materials, which is characterized in that
It is further included after step (2) described development：Drying.
8. such as claim 1~7 any one of them titanium-based and the surface modifying method of tantalum metal alkyl materials, which is characterized in that
Step (3) described etching gas include chloride and/or fluoro-gas；
Preferably, the chlorine-containing gas includes Cl2And/or BCl3；
Preferably, the fluoro-gas includes CF4；
Preferably, the etching gas further include inert gas；
Preferably, combination of the inert gas including any one in argon gas, nitrogen, helium or neon or at least two；
Preferably, step (3) described etching gas are argon gas, Cl2And BCl3Mixed gas；
Preferably, the flow of the argon gas is 0~90SCCM, the Cl2Flow be 0~100SCCM, the BCl3Flow
For 0~100SCCM, the Cl2Flow and the BCl3Flow difference when be 0；
Preferably, the time of step (3) described etching is 1~30min, preferably 5~15min.
9. a kind of surface has the medical metal material of nanotopology, which is characterized in that passes through such as claim 1~8 times
The surface modifying method of one titanium-based and tantalum metal alkyl materials is prepared.
10. surface as claimed in claim 9 has the purposes of the medical metal material of nanotopology, which is characterized in that institute
It states medical metal material of the surface with nanotopology and is used for orthopaedics implant, tooth-implanting and angiocarpy bracket.
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| CN110900925A (en) * | 2019-11-27 | 2020-03-24 | 南方科技大学 | Preparation method of PEEK with topological pattern on surface |
| CN113244004A (en) * | 2021-04-02 | 2021-08-13 | 浙江大学 | Implant surface modification device and method based on ultraviolet illumination patterning |
| CN113388822A (en) * | 2021-06-10 | 2021-09-14 | 南方科技大学 | Diamond film with topological pattern on surface and preparation method and application thereof |
| CN115029675A (en) * | 2022-05-30 | 2022-09-09 | 南方科技大学 | Topological patterned hydroxyapatite film, preparation method thereof and high-throughput screening method |
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| CN110900925A (en) * | 2019-11-27 | 2020-03-24 | 南方科技大学 | Preparation method of PEEK with topological pattern on surface |
| CN113244004A (en) * | 2021-04-02 | 2021-08-13 | 浙江大学 | Implant surface modification device and method based on ultraviolet illumination patterning |
| CN113388822A (en) * | 2021-06-10 | 2021-09-14 | 南方科技大学 | Diamond film with topological pattern on surface and preparation method and application thereof |
| CN115029675A (en) * | 2022-05-30 | 2022-09-09 | 南方科技大学 | Topological patterned hydroxyapatite film, preparation method thereof and high-throughput screening method |
| CN115029675B (en) * | 2022-05-30 | 2023-11-07 | 南方科技大学 | Topologically patterned hydroxyapatite film and preparation and high-throughput screening methods thereof |
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