CN103014814B - Electrochemical treatment method of increasing corrosion resistance of medical beta-type titanium alloy surface - Google Patents
Electrochemical treatment method of increasing corrosion resistance of medical beta-type titanium alloy surface Download PDFInfo
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Abstract
The invention relates to the technical field of surface treatment, and in particular relates to an electrochemical treatment method of increasing the corrosion resistance of a medical beta-type titanium alloy surface. A composite oxide amorphous film is prepared on the medical beta-type titanium alloy surface, and the method comprises the cathodic polarization and anodic passivation of the titanium alloy surface; firstly, the cathodic polarization is performed on the titanium alloy surface so as to remove the oxidation film which is formed on the alloy surface in the air and the dust pollutants attached on the oxidation film; and secondly, the anodic passivation is performed to generate the composite oxide amorphous film which is stable and compact. The electrochemical treatment method is suitable for the beta-type titanium alloy which is rich in elements such as Nb and Zr; the prepared passive film is in an amorphous state and has good biocompatibility, and the surface has high corrosion resistance, compactness and stability; and meanwhile, the prepared oxidation film layer is directly generated on a matrix through chemical and electrochemical principles, and conductive to enhancing the binding force between the matrix and the oxidation layer; and unrestricted by a matrix shape, the uniform passive film can be prepared on the matrix which has a complicated shape.
Description
Technical field
The present invention relates to technical field of surface, be specially a kind of electrochemical process for treating improving biomedical β-type Ti alloys surface corrosion resistance.
Background technology
Titanium is the year light metal climbing up world industry stage after World War II, is a nova in metallic substance kingdom.Titanium excellent property, rich reserves, from industrial value, resource longevity and development prospect, it is only second to iron, aluminium, is described as " the 3rd metal " that emerging.A large amount of element tasks and clinical study show, because titanium or titanium alloy has the property of high strength and low elastic modulus, and good biocompatibility, corrosion resistance nature and good mechanical property, make them in orthopedics and orthopaedics, have vast potential for future development.
The biological environment that the medicine equipment of implant into body works is very complicated physics, a chemical environment, except containing except the Multiple components such as body fluid, organic macromolecule, enzyme, free radical, cell, the Cl ion, F ion etc. that also there is different concns have the ion compared with vigorous erosion; In the particular surroundingss such as oral cavity, pH value can change in strongly-acid-slightly acidic-neutral zone that 3.2-7.3 is wider.Any metal or alloy is placed in fluid environment for a long time and all can corrodes; titanium alloy is no exception; and the passive film of alloy is the important barrier of protection alloy substrate; also be the first step of the biocompatibility ensureing alloy excellence, its performance has conclusive effect for the solidity to corrosion of alloy simultaneously.Therefore, surface treatment is carried out to titanium alloy surface, the thickness of controlled oxidization film and composition, improve the compactness of its surface film oxide, stability, thus alloy corrosion resistance and biocompatibility are strengthened, in application medically, vital effect is played to it, research emphasis is become to the modifying surface of medical titanium alloy.
Biomedical β-type Ti alloys is as the alloy representative studying comparatively deep in third generation titanium alloy, compared with a generation, two generation medical titanium alloys, no longer the elements such as insalubrious V, Al are added in third generation medical titanium alloy, the substitute is and health is not poisoned, and the elements such as Nb, Zr, Mo, Ta, Sn of alloy property can be improved, the alloy after adding is made to have higher tensile strength, fracture toughness property, better abrasion resistance properties.Titanium alloy is a kind of inert metal, and it can to loosen not fine and close oxide film by spontaneous formation one deck in atmosphere.Compared with the titanium alloy not adding these elements, in the alloy surface oxide film after third generation biomedical β-type Ti alloys with the addition of the elements such as Zr, Nb, Sn due to compound, define ZO
2, Nb
2o
5, SnO
2, making the density of oxide film increase erosion resistance increases.Therefore, the formation condition of controlled oxidization film, preparing thicker, finer and close, more stable oxide film becomes the effective ways improving third generation biomedical β-type Ti alloys corrosion resistance of surface.
Summary of the invention
The object of this invention is to provide a kind of electrochemical process for treating improving biomedical β-type Ti alloys surface corrosion resistance, its processing method is simple, with low cost, be rich in the composite oxides amorphous rete of the resistance to corrosion in body fluid of element biomedical β-type Ti alloys surface preparation such as Nb, Zr, the method can improve the corrosion resistance of surface being rich in the element biomedical β-type Ti alloys such as Nb, Zr greatly.
Technical scheme of the present invention is:
A kind of electrochemical process for treating improving biomedical β-type Ti alloys surface corrosion resistance, prepare composite oxides amorphous rete on the biomedical β-type Ti alloys surface of one or more alloying elements being rich in Nb, Zr, Sn, comprise the cathodic polarization to titanium alloy surface and anode passivation; First, by titanium alloy surface cathodic polarization, remove the alloy surface pollutent such as very thin (<5nm) of spontaneous formation and oxide film fine and close not and the dust that adheres in atmosphere above; Then, the anode passivation generation carrying out the long period is stablized and the composite oxides amorphous rete of densification.
The electrochemical process for treating of described raising biomedical β-type Ti alloys surface corrosion resistance, when biomedical β-type Ti alloys is Ti-Nb-Zr-Sn alloy, by carrying out cathodic polarization and anode passivation to titanium alloy, at the composite oxides passive film that its Surface Creation Ti-Nb-Zr-Sn is multicomponent amorphous; Internal layer is the composite oxides passivation film formed less than valency oxide compound that each element of Ti, Nb, Zr, Sn is corresponding, and contained by content and oxide compound, metallic element valence state diminishes from outside to inside gradually, and change in gradient, thickness is 4-18nm; Skin is the full valency oxide skin of Ti, Nb, Zr, Sn of thickness 1-2nm, and the composition of composite oxides passive film is TiO
2, Ti
2o
3, TiO, Nb
2o
5, NbO, SnO
2, ZrO
2, each constituent content and the valence state corresponding to oxide compound diminish from outside to inside gradually, change in gradient.
As shown in Figure 10, in the present invention, contained by each constituent content and oxide compound, the graded formation mechenism of metallic element valence state is:
According to the s-generation point defect model theory (PDM-II) of Macdonald, the reaction formula of metal/interfacial oxide film and oxide film/solution interface is respectively (1), (2), (3), (4), (5), (6) and (7).In oxide film forming process, cationvacancy produces at oxide film/solution interface place, and be consumed at metal/interfacial oxide film place, Lacking oxygen is then contrary.Therefore, cationvacancy from oxide film/solution interface to metal/migration of interfacial oxide film place, anion vacancy is then contrary, and the migration of Lacking oxygen result in the growth of oxide film.In reaction formula:
M---the atoms metal in metal m;
---the metallic cation room in oxide film dot matrix;
---the aninon gap in oxide film dot matrix;
---the oxygen anion room in oxide film dot matrix;
M
δ+(aq)---the positively charged ion at oxide film/solution interface place;
M
m---the atoms metal of metal sites in oxide film;
O
o---the Sauerstoffatom of oxygen position in oxide film;
---the oxide compound formed according to stoichiometric ratio;
In the process that oxide film thickens, the migration that growth due to oxide film is subject in the oxide film between metal/interfacial oxide film and oxide film/solution interface of metallic cation room and oxygen anion room controls, the migration in oxide film cationic room causes the dissolving of metal, finally causes oxide film to grow to matrix direction.Because the diffusion of electrolytic solution intermediate ion is slack-off along with the increase of oxide thickness, current density is caused to decline gradually.After current density declines, the electron exchange of oxidizing reaction is affected, and causes the reduction of oxide film cationic room valence state x, obtains the metallic cation M of lower valency
x+.Along with the increase of oxide thickness, formation has the oxide compound of lower valency as Ti
2o
3, TiO, NbO
2and NbO.And within the scope of the 1-2nm of oxide film surface, because oxygen is fully spread, then form the steady oxide TiO of full valency
2, Nb
2o
5, SnO
2, ZrO
2, thus make the oxide film component that alloy substrate is formed present graded.
Described cathodic polarization process is as follows: at a set temperature, and adopt three-electrode system, using biomedical β-type Ti alloys as working electrode, the platinized platinum being of a size of 2.5cm × 2.5cm is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer; After adding electrolytic solution, leave standstill 0.5-2h, after stable system, adopt the method for the constant potential polarization pattern of electrochemical workstation to deal with biomedical β-type Ti alloys; Described electrolytic solution take NaCl as ionogen, and concentration of electrolyte is 0.5-5wt%, and temperature is 20-50 DEG C; Voltage range be-2V to 0V, oxidization time is 1-30min.
The electrochemical process for treating of described raising biomedical β-type Ti alloys surface corrosion resistance, under identical cathodic polarization potential, along with the polarization time increases, biomedical β-type Ti alloys in atmosphere spontaneous formation very thin (<5nm) and oxide film fine and close not will dissolve gradually, by out exposed for the fresh biomedical β-type Ti alloys matrix surface containing elements such as Ti, Nb, Zr, Sn.
The electrochemical process for treating of described raising biomedical β-type Ti alloys surface corrosion resistance, titanium alloy surface after anticathode polarization process carries out anode passivation, described anode passivation process is as follows: at a set temperature, adopt three-electrode system, using biomedical β-type Ti alloys as working electrode, the platinized platinum being of a size of 2.5cm × 2.5cm is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer; After adding electrolytic solution, leave standstill 0.5-2h, after stable system, adopting the method for the constant potential polarization pattern of electrochemical workstation to deal with biomedical β-type Ti alloys, is the composite oxides passivation film of 5-20nm at its Surface Creation thickness; Described electrolytic solution take NaCl as ionogen, and concentration of electrolyte is 0.5-5Wt%, and voltage range is 0V to 3V, and the time is 0.5-5 hour; In process, temperature is 20-50 DEG C, and envrionment temperature keeps stable.
The electrochemical process for treating of described raising biomedical β-type Ti alloys surface corrosion resistance, under constant passivation potential, along with the increase of passivation time, (having removed oxide film) that do not have oxide film to cover fresh exposed biomedical β-type Ti alloys surface will be reoxidized, generate fresh stablizing and the passivation layer of densification gradually, and newly-generated passive film is non-crystalline state, film inner oxide valence state diminishes from outside to inside gradually, changes in gradient.
The electrochemical process for treating of described raising biomedical β-type Ti alloys surface corrosion resistance, when biomedical β-type Ti alloys is Ti-Nb-Zr-Sn alloy, from outermost full valency oxide compound TiO
2, Nb
2o
5, ZrO
2and SnO
2change to the oxide compound less than valency gradually, and be finally transitioned into matrix, thickness is 5-20nm, reaches the 3-5 of the oxide film of original spontaneous formation doubly.
In the present invention, after cathodic polarization, the oxide film of the surperficial spontaneous formation in atmosphere of biomedical β-type Ti alloys dissolves gradually, and the alloy substrate containing elements such as Ti, Nb, Zr, Sn is come out gradually.
In the present invention, after Passivation Treatment, the fresh exposed biomedical β-type Ti alloys surface of having removed oxide film will be reoxidized, and generate fresh stablizing and the passivation layer of densification gradually, and newly-generated passive film be non-crystalline state.
In the present invention, under different electrochemical parameter and time control parameter, can change in gradient at the oxide content of biomedical β-type Ti alloys Surface Creation composition corresponding to Ti, Nb, Zr, Sn element (comprising element valence contained by oxide compound), thickness is the form compact and stable composite oxides amorphous layer of 5-20nm, and thickness can reach original 3-5 doubly.
In the present invention, electrochemical workstation is Princeton 2273 electrochemical workstation.
In the present invention, thermostatic equipment is water-bath, and temperature error is ± 1 DEG C.
In the present invention, cathodic polarization and passivation are prepared electrolytic solution agents useful for same and are analytical pure.
Provided by the inventionly a kind ofly be rich in the electrochemical process for treating of biomedical β-type Ti alloys erosion resistance of the elements such as Nb, Zr, having the following advantages and beneficial effect:
1. the present invention can by the control of some influence factors in anticathode polarization process and anode passivation treating processes, obtain the composite amorphous type zone of oxidation with form compact and stable structure, film inner oxide composition is simple substance from full valency transition with thicknesses of layers change metal state gradually, and the thickness of oxide compound can control according to actual needs; The device simple used, simple to operate, passivating process does not need to stir, and does not need circulating water, can carry out under constant temperature.
2. the present invention adopts the method that cathodic polarization and anode passivation combine, when do not destroy matrix, not additional extra elements, ensure the security of beta titanium alloy when using in human body environment, increase the solidity to corrosion of its upper layer simultaneously.This treating processes film forming speed is fast, even film layer, and solidity to corrosion is good, and method is simple, the used time very short (≤7 hours).
3. the present invention is not by the restriction of substrate shapes, can prepare uniform coating on complex-shaped matrix.
4. the present invention both as the method in the biomedical β-type Ti alloys surface preparation of being rich in the elements such as Nb, Zr with the composite amorphous type passive film of form compact and stable structure, also can be used for carrying out modification to titanium dioxide film and improve its stability and solidity to corrosion.
5. contain Nb oxide compound containing a large amount of in the composite oxides passive film that prepared by the present invention, this also has huge benefit to the anti-corrosion capability improving titanium alloy surface.
In addition, prepare passive film by comparison with on other pure metal matrixes, the armorphous passivation film of the present invention in the composite oxides passivation film of biomedical β-type Ti alloys surface preparation being rich in the elements such as Nb, Zr has following features:
1. the passivation film thickness generated is controlled, and thickness is from 5nm to 20nm.
2. after the cathodic polarization of certain hour, remove the rete that original defect concentration is higher completely, ensure that newly-generated oxide film tends towards stability and densification, and there is good solidity to corrosion.
3., in the composite oxides passive film that prepared by the present invention, contained by the corresponding oxide content of each element of Ti, Nb, Zr, Sn and oxide compound, element valence diminishes from outside to inside gradually, changes in gradient.
4, the composite oxides passive film that prepared by the present invention is non-crystalline state, owing to not having crystal boundary, effectively prevents the diffusion of element, thus is protected by matrix alloy well, thus ensures higher solidity to corrosion.
Accompanying drawing explanation
Fig. 1 is the dynamic potential polarization curve contrast figure that employing the present invention carries out before and after Passivation Treatment on medical Ti-Nb-Zr-Sn alloy.
Fig. 2 is that electrochemical impedance spectroscopy (EIS) contrast adopting the present invention to carry out on medical Ti-Nb-Zr-Sn alloy before and after Passivation Treatment is schemed.Wherein, (a) figure is Nyquist (Nyquist) figure; B () figure is Byrd (Bode) phase angle and impedance chart.
The schematic circuit that Fig. 3 adopts for carrying out Equivalent Circuit Fitting to electrochemical impedance spectroscopy in Fig. 1 (EIS) data.
Atomic force microscope (AFM) the home position observation shape appearance figure that Fig. 4 (a)-(c) carries out before and after Passivation Treatment for employing the present invention on medical Ti-Nb-Zr-Sn alloy contrasts.Wherein, Fig. 4 (a) is formation passive film pattern spontaneous in air; Fig. 4 (b) is for adopting the surface topography of sample after cathodic polarization process in the present invention; Fig. 4 (c) by adopt after process of the present invention the pattern of formation passive film.
Fig. 5 is the TEM electron diffraction pattern adopting the present invention to carry out the armorphous passive film in Passivation Treatment rear surface on medical Ti-Nb-Zr-Sn alloy.
Fig. 6 (a)-Fig. 6 (b) carries out the variation diagram of the atomic percent before and after Passivation Treatment with thickness for adopting the present invention on medical Ti-Nb-Zr-Sn alloy.Wherein, Fig. 6 (a) is for before passivation; Fig. 6 (b) is for after passivation.
Fig. 7 is the XPS analysis collection of illustrative plates adopting the present invention to carry out Passivation Treatment front and rear surfaces Elemental redistribution on medical Ti-Nb-Zr-Sn alloy.Wherein, (a) figure is Ti2p; B () figure is Nb3d; C () figure is Sn3d; D () figure is Zr3d.
Fig. 8 (a)-Fig. 8 (b) schemes for adopting the present invention's electrochemical impedance spectroscopy (EIS) carried out on titanium-niobium alloy before and after Passivation Treatment to contrast.Wherein, Fig. 8 (a) is Nyquist figure; Fig. 8 (b) is Bode phase angle and impedance chart.
Fig. 9 (a)-Fig. 9 (b) schemes for adopting the present invention's electrochemical impedance spectroscopy (EIS) carried out on titanium-zirconium alloy before and after Passivation Treatment to contrast.Wherein, Fig. 9 (a) is Nyquist figure; Fig. 9 (b) is Bode phase angle and impedance chart.
Figure 10 is the reaction process schematic diagram of metal/interfacial oxide film and oxide film/solution interface.
Embodiment
Embodiment 1
Ti-24Nb-4Zr-8Sn alloy wire after thermal treatment is cut into the sample being of a size of 10 × 10 × 3mm, and with the ultrasonic cleaning each ten minutes one by one of acetone, dehydrated alcohol and deionized water, dries up in atmosphere.With epoxy resin, Ti-24Nb-4Zr-8Sn sample plastic packaging is made standard electrochemical sample, pre-mill is polished step by step with 800#, 1200#, 2000#SiC sand paper, and with dehydrated alcohol and deionized water rinsing, put into drying basin after drying up for subsequent use.
In the present embodiment, Chinese patent is shown in by Ti-24Nb-4Zr-8Sn alloy, application number: 200410092858.1, a kind of super elasticity low modulus titanium alloy and preparation and fabrication method.
Described cathodic polarization treatment process process is as follows:
Cathodic polarization mode, aqueous electrolyte liquid is 0.9wt%NaCl, and solution ph is about 6.5-7.2.Under 25 DEG C of conditions, adopt three-electrode system, using Ti-24Nb-4Zr-8Sn alloy as working electrode, the platinized platinum being of a size of 2.5cm × 2.5cm is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer.After adding the aqueous electrolyte liquid of about 350ml, leaving standstill 0.5-2h(the present embodiment is 1h), after stable system, adopt the method for the constant potential polarization pattern of electrochemical workstation to deal with Ti-24Nb-4Zr-8Sn alloy.Voltage range is-2V to 0V(the present embodiment is-1.2V), oxidization time is 1-30min(the present embodiment is 5min).
Titanium alloy surface after anticathode polarization process carries out anode passivation, and solution is consistent with the first step cathodic polarization, selects 0.9wt%NaCl, and voltage is 0.8V, and the time is 3 hours, and homo(io)thermism is 25 DEG C.At a set temperature, still three-electrode system is adopted, under constant passivation potential, along with the increase of passivation time, the fresh exposed beta titanium alloy surface not having oxide film to cover will be reoxidized, and generate fresh passivation layer, and newly-generated passive film is non-crystalline state, film inner oxide valence state diminishes from outside to inside gradually, changes in gradient, from outermost full valency oxide compound TiO
2, Nb
2o
5, ZrO
2and SnO
2gradually to matrix transition, thickness can reach 15nm.After passivation completes, use washed with de-ionized water specimen surface.
After the Passivation Treatment of 3 hours, the sample of Passivation Treatment is not yet carried out in contrast, its dynamic potential polarization curve is as shown in Figure 1: curve a is before passivation, curve b is after passivation, after Passivation Treatment, in potentiodynamic curves, active dissolution region is obviously shortened, and Ti-24Nb-4Zr-8Sn is provided with self-passivation ability, and its corrosion potential has risen to-0.15V from about-0.50V; Corrosion current reduces an order of magnitude from 4.80E-6A, reaches E-7A, and show that charge transfer quantity obviously reduces, the solidity to corrosion of material is significantly improved.The resistance value of passive film can reflect from Fig. 2-4.In Fig. 2 (a), the radius increase of circular curve shows, the degree of difficulty of electrode reaction increases, and solidity to corrosion improves.The intersection point of Fig. 2 (b) medium and low frequency place's curve and Y-axis significantly improves, and maximal phase angle value also increases, and shows that the stability of passive film improves.
Table 1, for adopting the contrast of Equivalent Circuit Fitting the data obtained shown in Fig. 3, can be seen from table, before and after passivation, characterizes the corrosion proof parameter charge transfer resistance R of passive film and has increased to 2.768 from 0.7609, increase about 3 times.Composition graphs 3 and table 1, through R (QR) Equivalent Circuit Fitting, charge transfer resistance R is from 0.7609M Ω cm
2fast lifting has arrived 2.768M Ω cm
2.The parameter Q value characterizing capacitance characteristic is also rapid in 29.30 μ Fcm
-2be reduced to 12.12 μ Fcm
-2, the defect concentration showing in passive film has had and has significantly declined.
Table 1
| R s/Ωcm 2 | R/MΩcm 2 | Q/μFcm -2 | n | |
| Before passivation | 21.42 | 0.7609 | 29.30 | 0.9502 |
| After passivation | 19.56 | 2.768 | 12.12 | 0.9515 |
In table, R
srepresent solution resistance, R represents polarization resistance, and Q represents normal phasing degree element, and n represents the degree that actual capacitance deviates from ideal capacitance, 0 < n < 1.
Fig. 4 is the change of specimen surface pattern before and after home position observation passivation, wherein: (a) figure is spontaneous formation passive film pattern in air; B () figure is the surface topography adopting sample after cathodic polarization process in the present invention; (c) figure by adopt after process of the present invention the pattern of formation passive film.Fig. 5 shows, and the passive film of generation is non-crystalline state.XPS surface analysis result shows, the composition of oxide film is TiO
2, Ti
2o
3, TiO, Nb
2o
5, NbO
2, NbO, SnO
2, ZrO
2, each constituent content and the valence state corresponding to oxide compound diminish from outside to inside gradually, change in gradient, as shown in Figure 6, Figure 7.
Result shows, after cathodic polarization and anode passivation process, the solidity to corrosion of alloy surface and stability have had significant raising, for ensureing that the biocompatibility of Ti-24Nb-4Zr-8Sn alloy is laid a good foundation.
Embodiment 2
Difference from Example 1 is:
Be 10mm by diameter, thickness is the Ti-25Nb(Nb25wt% of 1mm, Ti is remaining) sample is through acetone, dehydrated alcohol and deionized water ultrasonic cleaning after each ten minutes, standard electrochemical sample is made with epoxy resin plastic packaging, after pre-mill is polished step by step with 800#, 1200#, 2000#SiC sand paper, with dehydrated alcohol and deionized water rinsing, put into drying basin after drying up for subsequent use.
Described cathodic polarization treatment process process is as follows: cathodic polarization mode, and ionogen is the NaCl aqueous solution of 3.5wt%, and solution ph is about 4.5-6.5.Under 25 DEG C of conditions, adopt three-electrode system, using Ti-25Nb alloy as working electrode, the platinized platinum of big area (being of a size of 2.5cm × 2.5cm) is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer.After adding the aqueous electrolyte liquid of about 350ml, leaving standstill 0.5-2h(the present embodiment is 0.5h), after stable system, adopt the method for the constant potential polarization pattern of electrochemical workstation to deal with Ti-25Nb alloy.Voltage range is-2V to 0V(the present embodiment is-0.5V), oxidization time is 1-30min(the present embodiment is 15min).
Titanium alloy surface after anticathode polarization process carries out anode passivation, and solution is consistent with the first step cathodic polarization, selects simulate saliva, and the time is 0.5-5 hour (the present embodiment is 2h), and homo(io)thermism is 25 DEG C.
As shown in Figure 8, as can be seen from the low frequency value (0.01Hz) of Bode middle impedance, numerical value corresponding before Ti-25Nb alloy passivation is 0.3719M Ω cm to electrochemical impedance spectroscopy (EIS) curve corresponding with it
2, after Passivation Treatment, then significantly rise to 1.2573M Ω cm
2, reach 4 times more than.
Embodiment 3
Difference from Example 1 is:
Be 10mm by diameter, thickness is the Ti-25Zr(Zr25wt% of 1mm, Ti is remaining) sample is through acetone, dehydrated alcohol and deionized water ultrasonic cleaning after each ten minutes, standard electrochemical sample is made with epoxy resin plastic packaging, after pre-mill is polished step by step with 800#, 1200#, 2000#SiC sand paper, with dehydrated alcohol and deionized water rinsing, put into drying basin after drying up for subsequent use.
Described cathodic polarization treatment process process is as follows: cathodic polarization mode, and aqueous electrolyte liquid 0.9wt%NaCl solution, solution ph is about 6.5-7.2.Under 25 DEG C of conditions, adopt three-electrode system, using Ti-25Zr alloy as working electrode, the platinized platinum of big area (being of a size of 2.5cm × 2.5cm) is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer.After adding the aqueous electrolyte liquid of about 350ml, leaving standstill 0.5-2h(the present embodiment is 2h), after stable system, adopt the method for the constant potential polarization pattern of electrochemical workstation to deal with Ti-25Zr alloy.Voltage range is-2V to 0V(the present embodiment is-1.0V), oxidization time is 1-30min(the present embodiment is 10min).Titanium alloy surface after anticathode polarization process carries out anode passivation, and solution is consistent with the first step cathodic polarization, selects the NaCl solution of 0.9wt%, and the time is 0.5-5 hour (the present embodiment is 5h), and homo(io)thermism is 25 DEG C.
As shown in Figure 9, as can be seen from the low frequency value (0.01Hz) of Bode middle impedance, impedance value corresponding before Ti-25Zr alloy passivation is 0.4320M Ω cm to electrochemical impedance spectroscopy (EIS) curve corresponding with it
2, after Passivation Treatment, then significantly rise to 2.874M Ω cm
2, reach 6 times more than.
Result shows, the technology that the present invention adopts cathodic polarization and anode passivation to combine, and prepare the multicomponent amorphous composite oxides passive film of Ti-Nb-Zr-Sn at Ti-24Nb-4Zr-8Sn (wt.%) alloy surface, this passivation film thickness can reach 15nm.This passive film has excellent solidity to corrosion, compared with the oxide film of formation spontaneous in air, the method can be armorphous at the β type medical titanium alloy Surface Creation being rich in the elements such as Nb, Zr, Sn zone of oxidation, wherein element valence contained by the corresponding oxide content of each element of Ti, Nb, Zr and oxide compound diminishes from outside to inside gradually, changes in gradient.The multicomponent amorphous composite oxides passive film of Ti-Nb-Zr-Sn prepared by the present invention is to improving the solidity to corrosion of β type medical titanium alloy that is rich in the elements such as Nb, Zr, Sn and the biocompatibility on surface has great promotion meaning.
In addition, the present invention is also suitable for the β type medical titanium alloy be imbued with containing elements such as Nb, Zr, and the passive film anti-corrosion capability of preparation strengthens, and can improve the biocompatibility of alloy surface better, surface has very high compactness and stability; Meanwhile, this technique equipment used is simple and easy, simple to operate, and film forming is even, and thickness is controlled, can prepare the gradient passive film of different thickness according to actual needs by controlling the processing parameters such as working hour of anode passivation, operating voltage and temperature; In oxidising process, temperature remains at 50 ° of below C, the phase transformation that pyrolytic coating can be avoided to cause and embrittlement, and passivation film is directly created on matrix by chemistry and electrochemical principle, is conducive to strengthening the bonding force between matrix and passive film; Not by the restriction of substrate shapes, uniform passive film can be prepared on complex-shaped matrix.Therefore, the application of gradient bioactivation coating to the β type medical titanium alloy being rich in the elements such as Nb, Zr that the present invention generates will have very large promoter action.
Claims (5)
1. one kind is improved the electrochemical process for treating of biomedical β-type Ti alloys surface corrosion resistance, it is characterized in that: prepare composite oxides amorphous rete on the biomedical β-type Ti alloys surface of one or more alloying elements being rich in Nb, Zr, Sn, comprise the cathodic polarization to titanium alloy surface and anode passivation; First, by titanium alloy surface cathodic polarization, remove the alloy surface oxide film of spontaneous formation and the dust pollutant that adheres in atmosphere above; Then, carry out anode passivation generation stable and the composite oxides amorphous rete of densification;
Described cathodic polarization process is as follows: at a set temperature, and adopt three-electrode system, using biomedical β-type Ti alloys as working electrode, platinized platinum is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer; After adding electrolytic solution, leave standstill 0.5-2h, after stable system, adopt the method for the constant potential polarization pattern of electrochemical workstation to deal with biomedical β-type Ti alloys; Described electrolytic solution take NaCl as ionogen, and concentration of electrolyte is 0.5-5 wt %, and temperature is 20-50 DEG C; Voltage range be-2V to 0V, oxidization time is 1-30min;
Titanium alloy surface after anticathode polarization process carries out anode passivation, and described anode passivation process is as follows: at a set temperature, adopts three-electrode system, using biomedical β-type Ti alloys as working electrode, platinized platinum is supporting electrode, and saturated calomel electrode, as reference electrode, is placed in electrolyzer; After adding electrolytic solution, leave standstill 0.5-2h, after stable system, adopting the method for the constant potential polarization pattern of electrochemical workstation to deal with biomedical β-type Ti alloys, is the composite oxides passivation film of 5-20nm at its Surface Creation thickness; Described electrolytic solution take NaCl as ionogen, and concentration of electrolyte is 0.5-5 wt %, and voltage range is 0V to 3V, and the time is 0.5-5 hour; In process, electrolyte temperature is 20-50 DEG C, and envrionment temperature keeps stable.
2. according to the electrochemical process for treating of raising biomedical β-type Ti alloys surface corrosion resistance according to claim 1, it is characterized in that, when biomedical β-type Ti alloys is Ti-Nb-Zr-Sn alloy, by carrying out cathodic polarization and anode passivation to titanium alloy, at the composite oxides passive film that its Surface Creation Ti-Nb-Zr-Sn is multicomponent amorphous; Internal layer is the composite oxides passivation film formed less than valency oxide compound that each element of Ti, Nb, Zr, Sn is corresponding, and contained by content and oxide compound, metallic element valence state diminishes from outside to inside gradually, and change in gradient, thickness is 4-18nm; Skin is the full valency oxide skin of Ti, Nb, Zr, Sn of thickness 1-2nm, and the composition of composite oxides passive film is TiO
2, Ti
2o
3, TiO, Nb
2o
5, NbO
2, NbO, SnO
2, ZrO
2, each constituent content and the valence state corresponding to oxide compound diminish from outside to inside gradually, change in gradient.
3. according to the electrochemical process for treating of raising biomedical β-type Ti alloys surface corrosion resistance according to claim 1, it is characterized in that, under identical cathodic polarization potential, along with the polarization time increases, the oxide film of biomedical β-type Ti alloys spontaneous formation in atmosphere will dissolve, gradually by out exposed for fresh biomedical β-type Ti alloys matrix surface.
4. according to the electrochemical process for treating of raising biomedical β-type Ti alloys surface corrosion resistance according to claim 1, it is characterized in that, under constant passivation potential, along with the increase of passivation time, the fresh exposed biomedical β-type Ti alloys surface not having oxide film to cover will be reoxidized, and generate fresh passivation layer, and newly-generated passive film be non-crystalline state, film inner oxide valence state diminishes from outside to inside gradually, changes in gradient.
5. according to the electrochemical process for treating of raising biomedical β-type Ti alloys surface corrosion resistance according to claim 4, it is characterized in that, when biomedical β-type Ti alloys is Ti-Nb-Zr-Sn alloy, from outermost full valency oxide compound TiO
2, Nb
2o
5, ZrO
2and SnO
2change to the oxide compound less than valency gradually, and be finally transitioned into matrix, thickness is 5-20nm, reaches the 3-5 of the oxide film of original spontaneous formation doubly.
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| CN107142444B (en) * | 2017-03-28 | 2019-09-06 | 广西大学 | A kind of preparation method of the medical zircaloy of β type of surface oxidation |
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| CN109652838B (en) * | 2018-12-27 | 2021-05-18 | 浙江工业大学 | Titanium-niobium alloy surface anodic oxidation coloring method |
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