CN103364243A - Preparation method of titanium alloy surface passivation film transmission observation sample - Google Patents
Preparation method of titanium alloy surface passivation film transmission observation sample Download PDFInfo
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Abstract
The invention relates to the field of preparation of a transmission sample, and in particular to a preparation method of a titanium alloy surface passivation film transmission observation sample. The method comprises the following steps of: (1) performing double-spray thinning treatment on a transmission sample with diameter of 3mm and thickness of 40-50 microns polished by sand paper in acid liquor at -20to -30 DEG C to prepare a transmission sample with thin region thickness of about 30nm-100nm and uniform distribution; (2) performing cathodic polarization on the transmission sample subjected to the double spray in electrolyte under the condition of -0.5V to -1.5V for about 1-10 min so as to remove an oxide film spontaneously formed on the surface of the sample in air; and (3) performing anodic passivation treatment on the alloy sample under the condition of 0 to 2V for 0.5-5 hours to fully oxidize the alloy surface so as to form a passivation film uniformly distributed at the thin region of the transmission sample. The fully passivated thin region is completely made from metal oxide and can be free from the influence of an alloy phase of a matrix, and thus the phase composition and the element distribution of the passivation film are easily observed. The preparation method is suitable for preparing of the transmission observation sample of the passivation film of titanium, titanium alloy and the like with thickness of only several nanometers.
Description
Technical field:
The present invention relates to the transmission sample preparation field, be specially a kind of preparation method of titanium alloy surface passivating film viewed in transmittance sample.
Background technology:
When metal or alloy places the medium such as air or solution, can be spontaneous and these medium effects, generate one deck solid product film at material surface.People self are insoluble in medium wherein suppressing anodic dissolution processes this diaphragm is called passivating film.Passivating film becomes independent and exists mutually, is the compound of oxidized metal substantially, and generally, the thickness of passivating film is limited, compact structure, covering performance is good and can be adsorbed on the metal surface securely.It plays a part metal and corrosive medium are separated fully, prevents that metal from contacting with corrosive medium, reaches etch-proof effect thereby make metal substantially stop dissolving formation passive state.Therefore, the performance of metal or alloy surface passivated membrane is directly connected to device result of use and serviceable life in the environment under arms.
At present, research method for the alloy passivation film mainly adopts some surface analysis means, such as the electrokinetic potential polarization curve in the Electrochemical Detection (Potentiodynamic Polarization curve), Mott-Schottky curve, electrochemical impedance spectroscopy (Electrochemical Impedance Spectroscopy, EIS) etc.; And conventional x-ray photoelectron power spectrum (X-ray Photoelectron Spectroscopy, XPS), scanning electron microscope (Scanning ElectronMicroscopy, SEM), atomic force microscope (Atomic Force Microscopy, AFM) etc.Can effectively detect the pattern of material surface, compound valence state, the performance index such as corrosion stability by these detection meanss.But the thickness of passivating film only is micron dimension or thinner, then can't obtain for information such as the phase composition of passivating film and crystal structures, and is very difficult to the research of its microstructure, and many characterizing methods are difficult to adopt.Obtain these information of passivating film, need to be by transmission electron microscope (Transmission Electron Microscope, TEM).
The transmission electron microscopy analysis is one of most important means of membraneous material microstructure study.At present, the passivating film sample that is used for transmission electron microscope observing adopts the method for preparing cross-sectional sample usually.Reach the alloy of micron level for passivation film thickness such as stainless steel, carbon steels, the preparation cross-sectional sample can effectively be observed the thicknesses of layers, element distribution of alloy etc.But the preparation very complicated of cross-sectional sample, long expense consuming time is high, and success ratio is low, is a kind of method that is very difficult to grasp.
Titanium or titanium alloy has fabulous self-passivation ability, and the alloy surface of fresh scraping can moment oxidation occur in air, generates new diaphragm.Because its surface passivated membrane defect density that forms in air is higher, and thickness only be 2nm～8nm, also can't finish research to its surface microscopic performance even employing prepares the method for cross section transmission sample.Therefore, the research of titanium or titanium alloy aspect passivation film structure relatively lags behind, demand at present developing a kind of preparation of transmission samples for the thinner alloy of surface passivated membrane simple to operation urgently, as the effective means of research alloy passivation film phase composition and structure.
Summary of the invention:
The preparation method who the purpose of this invention is to provide a kind of titanium alloy surface passivating film viewed in transmittance sample solves the problems such as the cost height, complex process, the success ratio that exist in the transmission sample technology of preparing of existing passivating film cross section are low.The titanium that adopts the method to prepare to be applicable to the very thin films layer thickness or the plane transmission sample of titanium alloy material are used for observing at transmission electron microscope pattern, phase composition and the alloying elements distribution of alloy surface passivating film.The method technique is simple, cost is low, grasp easily, success ratio is high, the transmission sample that obtains has that thin district distributes evenly, the surface film passivation fully, become phase effect good, be convenient to the plurality of advantages such as long preservation, have boundless application prospect at research titanium alloy surface passivating film pattern and structure field.
Technical scheme of the present invention:
A kind of preparation method of titanium alloy surface passivating film viewed in transmittance sample, the preparation of this kind transmission sample comprises two spray reduction processing, and the good transmission sample of two sprays is made cathodic polarization and follow-up three aspects of anodic passivity, concrete steps are as follows:
(1) two spray reduction processing
To place the acid solution of cooled with liquid nitrogen through the titanium alloy sample of sand papering, regulate temperature, flow velocity and transmittance, sample is done two spray reduction processing, prepares thin district thickness at the transmission sample of 30nm-100nm;
(2) cathodic polarization
Thin district distributes uniform sample as working electrode after selecting two sprays, adopt traditional three-electrode system that sample is carried out electrochemical treatment, under the constant potential polarization module of electrochemical workstation, apply voltage and remove alloy surface larger oxide film of the defect density of spontaneous formation in air;
(3) anodic passivity
Sample after the cathodic polarization is made Passivation Treatment in the interval scope of passivation potential, obtain the transmission sample that thin district complete oxidation and oxide are evenly distributed, be directly used in the film phase composition of transmission electron microscope observing alloy passivation and structure.
In the described step (1), with 800#～2000#SiC sand paper alloy sample of polishing step by step, make its thickness be positioned at 40 μ m-50 μ m intervals, it is the circular disc test specimen of 3mm that punching becomes diameter, and grinds off the burr that punching produces.
In the described step (1), the titanium alloy sample that polishing is good places the sample cell of two spraying equipments, the acid solution for the treatment of cooled with liquid nitrogen is positioned at-20 ℃～-30 ℃ temperature range, acid solution is the mixed solution that contains perchloric acid 6wt%, methyl alcohol 59wt% and normal butyl alcohol 35wt%, regulate flow velocity and transmittance sample is done two spray reduction processing, prepare thin district thickness at the transmission sample of 30nm～100nm.
In the described step (2), connect and the Φ of transmission sample alloy of the same race≤0.5mm tinsel with copper conductor, and use epoxy encapsulation, the tinsel of only reserving 4mm-8mm length is exposed to the outer end, be convenient to contact with transmission sample, effectively avoid the generation of bimetallic corrosion; Select the rear thin district of two sprays gradually transition and equally distributed transmission sample, with conducting resinl bonding transmission sample and tinsel, guarantee that electric conductivity is good.
In the described step (2), at ambient temperature, adopt traditional three-electrode system, the electrode of binder alloy transmission sample is as working electrode, and saturated calomel electrode is as contrast electrode, and platinized platinum is as auxiliary electrode; This process at first places electrode electrolytic cell to leave standstill to stable state, and the duration is 0.5h-2h; Potentiostatic mode with electrochemical workstation applies current potential to it, and the described electrolytic solution of this process is take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%, and potential range is-0.5V～-1.5V, the duration is 1min～10min.
In the described step (3), sample after the anticathode polarization is processed carries out follow-up anodic passivity, described anodic passivity process is as follows: adopt the three-electrode system identical with step (2), the transmission sample after anticathode polarization under the constant potential polarization pattern of electrochemical workstation is done anodic passivity; The described electrolytic solution of this process is take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%, and voltage range is 0V～2V, and the time is 0.5-5 hour; In the process, it is stable that electrolyte temperature keeps.
In the described step (3), anodic passivity is taken off transmission sample after finishing, and cleans with deionized water and alcohol, and after filter paper blotted, air-dry in air, it was for subsequent use to put into sample box.
Described alloy is pure titanium or various titanium alloy, and wherein titanium alloy is the Ti-24Nb-4Zr-8Sn of Ti-6Al-4V, Ti-Nb, Ti-24Nb-4Zr-8Sn or nanometer.
Beneficial effect of the present invention:
1, the equipment of the present invention's use is two spray attenuate instrument and electrochemical workstations, and method technique is simple, and cost is low, and success ratio is high, applicable to most of titanium alloys.The method is comprised of following step: (1) will be that 3mm thickness is that the transmission sample of 40 μ m-50 μ m is made two spray reduction processing, the transmission samples of preparing the about 30nm～100nm of thin district thickness and being evenly distributed in-20 ℃～-30 ℃ acid solution through the diameter of sand papering; (2) transmission sample after two sprays is put into electrolytic solution-0.5V～-do cathodic polarization under the 1.5V condition, about 1min～10min of duration is to remove the oxide film of sample surfaces spontaneous formation in air; (3) be right after previous step, the alloy sample is done anodic passivity and is processed under 0V～2V condition, continue 0.5h-5h, makes the abundant oxidation of alloy surface, forms the passivating film that is uniformly distributed in the thin district of transmission sample.All be metal oxide in the thin district of passivation fully, can not affected mutually by matrix alloy, easily observe passivating film phase composition and element and distribute.
2, cathodic polarization and the technological parameters such as the time of anodic passivity process, current potential of the present invention by the control plane transmission sample, can prepare as required the observation titanium alloy passivating film transmission sample of different passivation areas, thereby phase composition and micromechanism by transmission electron microscope observing alloy passivation film, avoid preparing Complicated Flow and the low success rate of film transmission sample, broken and observed for a long time the routine that passivating film must prepare film sample.The method is specially adapted to study as thin as a wafer, and the transmission electron microscope observing of passivating film (thickness is less than 50nm) institutional framework has boundless application prospect in fields such as film, surface, coatings.
Description of drawings:
Fig. 1: the connected mode of working electrode in cathodic polarization and the anodic passivity process; Among the figure, 1 copper conductor; 2 epoxy resin; 3 tinsels; 4 transmission samples;
Fig. 2: pure titanium is processed rear surface passivating film pattern through the inventive method; Among the figure, the A point is complete passivation region, and the B point is passivation-not passivation zone of transition, and the C point is passivation-not passivation zone of transition, and the D point is passivation region not;
Fig. 3: the diffraction spot of pure titanium selected diffraction; A wherein, B, C, D be A point, B point, C point, the D point in the corresponding diagram 2 respectively, and the A point is complete passivation region, and the B point is passivation-not passivation zone of transition, and the C point is passivation-not passivation zone of transition, and the D point is passivation region not;
Fig. 4: the passivating film pattern of Ti-6Al-4V alloy after the inventive method is processed;
Fig. 5: the amorphous state diffraction spot of Ti-6Al-4V alloy passivation film;
Fig. 6: the passivating film pattern of Ti-25Nb alloy after the inventive method is processed;
Fig. 7: the amorphous state diffraction spot of Ti-25Nb alloy passivation film;
Fig. 8: the passivating film pattern of Ti-24Nb-4Zr-8Sn alloy (the about 80 μ m of crystallite dimension) after the inventive method is processed;
Fig. 9: the diffraction spot of Ti-24Nb-4Zr-8Sn alloy (the about 80 μ m of crystallite dimension) selected diffraction; A wherein, B, C, D be A point, B point, C point, the D point in the corresponding diagram 8 respectively, and the A point is complete passivation region, and the B point is passivation-not passivation zone of transition, and the C point is passivation-not passivation zone of transition, and the D point is passivation region not;
Figure 10: Ti-24Nb-4Zr-8Sn alloy (the about 80 μ m of crystallite dimension) film interior element distributes; Wherein, (a) shape appearance figure of scanning area, (b) distribution of O element, (c) distribution of Ti element, (d) distribution of Nb element;
Figure 11: Ti-24Nb-4Zr-8Sn nanometer crystal alloy (crystallite dimension is less than 50nm) is processed post-passivation film pattern through the inventive method;
Figure 12: the diffraction spot of Ti-24Nb-4Zr-8Sn nanometer crystal alloy (crystallite dimension is less than 50nm) selected diffraction; A wherein, B, C, D be A point, B point, C point, the D point among corresponding Figure 11 respectively, and the A point is complete passivation region, and the B point is passivation-not passivation zone of transition, and the C point is passivation-not passivation zone of transition, and the D point is passivation region not;
Figure 13: Ti-24Nb-4Zr-8Sn nanometer crystal alloy (crystallite dimension is less than 50nm) film interior element distributes; Wherein, (a) shape appearance figure of scanning area, (b) distribution of O element, (c) distribution of Ti element, (d) distribution of Nb element.
Embodiment:
The preparation method of titanium alloy surface passivating film viewed in transmittance sample of the present invention, its preparation process comprise the three parts such as conventional two spray reduction processing, cathodic polarization, anodic passivity, and concrete steps are as follows:
(1) two spray reduction processing
Two spray reductions are adopted in the thin district preparation of alloy transmission sample, and Preparation equipment is " the two spray of Denmark Struers company's T enupol-5 attenuate instrument " device.
Among the present invention, the alloy transmission sample is the conventional planar sample of disc-shaped, and diameter is Φ 3mm, and before two spray attenuates, sample is polished step by step through 800#～2000#SiC silicon carbide paper, to thickness be 40 μ m～50 μ m.Use the constant two spray temperature of liquid nitrogen to be positioned at-20 ℃～-30 ℃ interval, (flow rates is 80ml/min～100ml/min) and transmittance (range of transmittance is 30%-60%), prepares thin district thickness at 30nm-100nm and equally distributed transmission sample to regulate flow velocity.
Among the present invention, the used corrosive liquid of two spray attenuates constitutes: perchloric acid 6wt%; Methyl alcohol 59wt%; Normal butyl alcohol 35wt%.
(2) cathodic polarization
Among the present invention, the employed equipment of the cathodic polarization of alloy transmission sample and anodic passivity is that the U.S. produces Princeton 2273 electrochemical workstations.
Among the present invention, the cathodic polarization of alloy transmission sample and anodic passivity prepare the electrolytic solution agents useful for same be analyze pure.
At first, use copper conductor 1 to connect with transmission sample 4 with the tinsel 3(Φ of material≤0.5mm), and encapsulate with epoxy resin 2, the tinsel 3 of only reserving the about 4mm-8mm of length is exposed to the outer end, be convenient to contact with transmission sample 4, avoid occuring bimetallic corrosion, as shown in Figure 1.Select the rear thin district of two sprays gradually transition and equally distributed transmission sample 4, with conducting resinl bonding transmission sample 4 and tinsel 3, guarantee that electric conductivity is good.
Then, the transmission sample that connects is put into electrolytic cell as working electrode, put into saturated calomel electrode and Pt sheet, as contrast electrode and auxiliary electrode, form three-electrode system.Topple over 350ml electrolytic solution, leave standstill to stable state, the duration is 0.5h-2h.The described electrolytic solution of this process is take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%.
At last, with the potentiostatic mode of electrochemical workstation it being applied current potential, potential range is-1.5V～-0.5V, the duration is 1min～10min.
(3) anodic passivity
Sample after the anticathode polarization is processed carries out follow-up anodic passivity, adopts the three-electrode system identical with step (2), and the transmission sample after anticathode polarization under the constant potential polarization pattern of electrochemical workstation is done anodic passivity; This process can make described electrolytic solution take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%, and voltage range is 0V～2V, and the time is 0.5-5 hour; In the process, it is stable that electrolyte temperature keeps.
Anodic passivity is taken off transmission sample after finishing, and cleans with deionized water and alcohol, and after filter paper blotted, air-dry in air, it was for subsequent use to put into sample box.
The present invention is applicable to have titanium or the titanium alloy material of well passivated performance, such as Ti-24Nb-4Zr-8Sn alloy of pure titanium, Ti-6Al-4V, Ti-Nb, Ti-24Nb-4Zr-8Sn or nanometer etc.Adopt the titanium alloy surface oxide passivating film viewed in transmittance sample of the inventive method preparation, the about 50nm～200nm of its complete passivation region thin area edge of distance, scope changes with passivation time.Adopt the transmission sample of the home position observation alloy surface passivating film of the inventive method preparation, phase composition and the element that can easily observe passivating film on planar sample distribute.
Below by embodiment and accompanying drawing the present invention is further elaborated.
Embodiment 1
Utilize " two spray reduction " to prepare the equally distributed pure titanium plane transmission sample in thin district, after the clean dry, connect according to as shown in Figure 1 mode.Adopt three-electrode system, access links the electrode of plane transmission sample as working electrode, carries out cathodic polarization under the potentiostatic mode of electrochemical workstation.Leave standstill about 1h open circuit potential is tended towards stability, then apply-1V voltage, duration 5min removes surface film oxide; Add subsequently 1.0V voltage, do anodic passivity, about 2h of duration; Obtain the transmission sample of the complete passivation of thin district's front end, as shown in Figure 2.In the present embodiment, the used electrolytic solution of cathodic polarization, anodic passivity is take NaCl as electrolyte, and concentration of electrolyte is 0.5wt%.
In the present embodiment, the pure Ti passivation structure for preparing, in thin district near hole place complete oxidation, and gradually to the matrix alloy transition, because pure titanyl compound is amorphous state, from the diffracting spectrum of Fig. 3, can see phase structure gradually transition from crystalline state to amorphous state of oxide, amorphous area size changes with passivation time.
Embodiment 2
Utilize " two spray reduction " to prepare thin district equally distributed Ti-6Al-4V alloy plane transmission sample, after the clean dry, connect according to as shown in Figure 1 mode.Adopt three-electrode system, access links the electrode of plane transmission sample as working electrode, carries out cathodic polarization under the potentiostatic mode of electrochemical workstation.Leave standstill about 2h open circuit potential is tended towards stability, then apply-0.8V voltage, duration 5min removes surface film oxide; Add subsequently 0.5V voltage, do anodic passivity, about 4h of duration; Obtain the transmission sample of the complete passivation of thin district's front end, as shown in Figure 4.In the present embodiment, the used electrolytic solution of cathodic polarization, anodic passivity is take NaCl as electrolyte, and concentration of electrolyte is 1wt%.
In the present embodiment, the Ti-6Al-4V alloy passivation membrane structure for preparing, in thin district near hole place complete oxidation, and gradually to the matrix alloy transition, because the oxide of Ti-6Al-4V alloy is amorphous state, from the diffracting spectrum of Fig. 5, can see that its diffraction spot shows the distinctive haloing of amorphous alloy.
Embodiment 3
Utilize " two spray reduction " to prepare thin district equally distributed Ti-25Nb alloy plane transmission sample, after the clean dry, connect according to as shown in Figure 1 mode.Adopt three-electrode system, access links the electrode of plane transmission sample as working electrode, carries out cathodic polarization under the potentiostatic mode of electrochemical workstation.Leave standstill about 1.5h open circuit potential is tended towards stability, then apply-1.0V voltage, duration 5min removes surface film oxide; Add subsequently 0.8V voltage, do anodic passivity, about 2.5h of duration; Obtain the transmission sample of the complete passivation of thin district's front end, as shown in Figure 6.In the present embodiment, the used electrolytic solution of cathodic polarization, anodic passivity is take NaCl as electrolyte, and concentration of electrolyte is 2wt%.
In the present embodiment, the Ti-25Nb alloy passivation membrane structure for preparing, in thin district near hole place complete oxidation, and gradually to the matrix alloy transition, because the oxide of Ti-25Nb alloy is amorphous state, from the diffracting spectrum of Fig. 7, can see that its diffraction spot shows the distinctive haloing of amorphous alloy.
Embodiment 4
Utilize " two spray reduction " to prepare thin district equally distributed Ti-24Nb-4Zr-8Sn coarse-grain alloy (the about 80 μ m of crystallite dimension) plane transmission sample, after the clean dry, connect according to as shown in Figure 1 mode.Adopt three-electrode system, access links the electrode of plane transmission sample as working electrode, carries out cathodic polarization under the potentiostatic mode of electrochemical workstation.Leave standstill about 1h open circuit potential is tended towards stability, then apply-0.8V voltage, duration 10min removes surface film oxide; Add subsequently 1.5V voltage, do anodic passivity, about 3h of duration; Obtain the transmission sample of the complete passivation of thin district's front end, as shown in Figure 8.In the present embodiment, the used electrolytic solution of cathodic polarization, anodic passivity is take NaCl as electrolyte, and concentration of electrolyte is 3wt%.
In the present embodiment, the Ti-24Nb-4Zr-8Sn coarse-grain alloy passivation membrane structure for preparing, in thin district near hole place complete oxidation, and gradually to the matrix alloy transition, because the oxide of Ti-24Nb-4Zr-8Sn coarse-grain alloy is amorphous state, from the diffracting spectrum of Fig. 9, can see phase structure gradually transition from crystalline state to amorphous state of oxide, amorphous area size changes with passivation time.Figure 10 is that the EDS face is swept the result, and the element that can qualitatively judge in the thin district of this alloy passivating film distributes.
Embodiment 5
Utilize " two spray reduction " to prepare the equally distributed Ti-24Nb-4Zr-8Sn nanometer crystal alloy in thin district (crystallite dimension is less than about 50nm) plane transmission sample, after the clean dry, connect according to as shown in Figure 1 mode.Adopt three-electrode system, access links the electrode of plane transmission sample as working electrode, carries out cathodic polarization under the potentiostatic mode of electrochemical workstation.Leave standstill about 1h open circuit potential is tended towards stability, then apply-1.2V voltage, duration 6min removes surface film oxide; Add subsequently 1.2V voltage, do anodic passivity, about 4h of duration; Obtain the transmission sample of the complete passivation of thin district's front end, as shown in figure 11.In the present embodiment, the used electrolytic solution of cathodic polarization, anodic passivity is take NaCl as electrolyte, and concentration of electrolyte is 4wt%.
In the present embodiment, the Ti-24Nb-4Zr-8Sn coarse-grain alloy passivation membrane structure for preparing, in thin district near hole place complete oxidation, and gradually to the matrix alloy transition, because the oxide of Ti-24Nb-4Zr-8Sn nanometer crystal alloy is amorphous state, from the diffracting spectrum of Figure 12, can see phase structure gradually transition from crystalline state to amorphous state of oxide, amorphous area size changes with passivation time.Figure 13 is that the EDS face is swept the result, and the element that can qualitatively judge in the thin district of this alloy passivating film distributes.
Embodiment result shows, method of the present invention is simple to operation, react controlled fast, become phase effect good, can fast and effeciently prepare the sample for the oxide passivation film viewed in transmittance, being specially adapted to the titanium or titanium alloy equal thickness only is the viewed in transmittance sample preparation of the passivating film of several nanometers, can avoid preparing the complicated and expensive methods such as cross-sectional sample, simple, intuitive ground carries out transmission electron microscope observing to the microscopic characteristics of passivating film fast, has important impetus for studying the oxide passivation film micromechanism of thickness less than 50nm.
Claims (9)
1. the preparation method of a titanium alloy surface passivating film viewed in transmittance sample is characterized in that, the preparation of this kind transmission sample comprises two spray reduction processing, and the good transmission sample of two sprays is made cathodic polarization and follow-up three aspects of anodic passivity, and concrete steps are as follows:
(1) two spray reduction processing
To place the acid solution of cooled with liquid nitrogen through the titanium alloy sample of sand papering, regulate temperature, flow velocity and transmittance, sample is done two spray reduction processing, prepares thin district thickness at the transmission sample of 30nm-100nm;
(2) cathodic polarization
Thin district distributes uniform sample as working electrode after selecting two sprays, adopt traditional three-electrode system that sample is carried out electrochemical treatment, under the constant potential polarization module of electrochemical workstation, apply voltage and remove alloy surface larger oxide film of the defect density of spontaneous formation in air;
(3) anodic passivity
Sample after the cathodic polarization is made Passivation Treatment in the interval scope of passivation potential, obtain the transmission sample that thin district complete oxidation and oxide are evenly distributed, be directly used in the film phase composition of transmission electron microscope observing alloy passivation and structure.
2. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (1), with 800#～2000#SiC sand paper alloy sample of polishing step by step, make its thickness be positioned at 40 μ m-50 μ m intervals, it is the circular disc test specimen of 3mm that punching becomes diameter, and grinds off the burr that punching produces.
3. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (1), the titanium alloy sample that polishing is good places the sample cell of two spraying equipments, the acid solution for the treatment of cooled with liquid nitrogen is positioned at-20 ℃～-30 ℃ temperature range, acid solution is the mixed solution that contains perchloric acid 6wt%, methyl alcohol 59wt% and normal butyl alcohol 35wt%, regulate flow velocity and transmittance sample is done two spray reduction processing, prepare thin district thickness at the transmission sample of 30nm～100nm.
4. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (2), connect and the Φ of transmission sample alloy of the same race≤0.5mm tinsel with copper conductor, and use epoxy encapsulation, the tinsel of only reserving 4mm-8mm length is exposed to the outer end, be convenient to contact with transmission sample, effectively avoid the generation of bimetallic corrosion; Select the rear thin district of two sprays gradually transition and equally distributed transmission sample, with conducting resinl bonding transmission sample and tinsel, guarantee that electric conductivity is good.
5. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (2), at ambient temperature, adopt traditional three-electrode system, the electrode of binder alloy transmission sample is as working electrode, saturated calomel electrode is as contrast electrode, and platinized platinum is as auxiliary electrode; This process at first places electrode electrolytic cell to leave standstill to stable state, and the duration is 0.5h-2h; Potentiostatic mode with electrochemical workstation applies current potential to it, and the described electrolytic solution of this process is take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%, and potential range is-0.5V～-1.5V, the duration is 1min～10min.
6. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (3), sample after the anticathode polarization is processed carries out follow-up anodic passivity, described anodic passivity process is as follows: adopt the three-electrode system identical with step (2), the transmission sample after anticathode polarization under the constant potential polarization pattern of electrochemical workstation is done anodic passivity; The described electrolytic solution of this process is take NaCl as electrolyte, and concentration of electrolyte is 0.5-5wt%, and voltage range is 0V～2V, and the time is 0.5-5 hour; In the process, it is stable that electrolyte temperature keeps.
7. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: in the described step (3), after anodic passivity finishes, take off transmission sample, clean with deionized water and alcohol, after filter paper blots, air-dry in air, it is for subsequent use to put into sample box.
8. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 1, it is characterized in that: described alloy is pure titanium or various titanium alloy.
9. according to the preparation method of titanium alloy surface passivating film viewed in transmittance sample claimed in claim 8, it is characterized in that: described titanium alloy is the Ti-24Nb-4Zr-8Sn of Ti-6Al-4V, Ti-Nb, Ti-24Nb-4Zr-8Sn or nanometer.
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| CN104297036A (en) * | 2014-10-24 | 2015-01-21 | 天津大学 | Preparation method of transmission electron microscope metal sample |
| CN104913957A (en) * | 2015-05-04 | 2015-09-16 | 中国石油化工股份有限公司 | Preparation method for TEM in-situ observation material matrix/passivation film interface structure sample |
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| CN103592171A (en) * | 2013-11-27 | 2014-02-19 | 内蒙古包钢钢联股份有限公司 | Method for preparing transmission electron microscope sample |
| CN104297036A (en) * | 2014-10-24 | 2015-01-21 | 天津大学 | Preparation method of transmission electron microscope metal sample |
| CN104913957A (en) * | 2015-05-04 | 2015-09-16 | 中国石油化工股份有限公司 | Preparation method for TEM in-situ observation material matrix/passivation film interface structure sample |
| CN108181156A (en) * | 2016-12-08 | 2018-06-19 | 北京有色金属研究总院 | A kind of copper alloy preparation method of sample for EBSD tests |
| CN109632916A (en) * | 2018-12-20 | 2019-04-16 | 西安铂力特增材技术股份有限公司 | A method of measurement increasing material manufacturing titanium alloy surface Stability of Passive Film |
| CN109852957A (en) * | 2018-12-20 | 2019-06-07 | 西安铂力特增材技术股份有限公司 | A kind of titanium alloy surface method of modifying for increasing material manufacturing |
| CN109900630A (en) * | 2019-01-31 | 2019-06-18 | 中国科学院金属研究所 | It is a kind of to evaluate complicated metal pair to the test device and method of galvanic corrosion |
| CN113092506A (en) * | 2021-03-10 | 2021-07-09 | 南京理工大学 | Transmission electron microscope sample preparation device and method capable of positioning thin area position |
| CN113418762A (en) * | 2021-06-12 | 2021-09-21 | 西北工业大学 | Preparation method of transmission electron microscope sample for observing nano structure of passivation film |
| KR20230032180A (en) * | 2021-08-30 | 2023-03-07 | 창원대학교 산학협력단 | Method and for producing NaCl standard samples for transmission electron microscopy |
| KR102563103B1 (en) | 2021-08-30 | 2023-08-02 | 창원대학교 산학협력단 | Method and for producing NaCl standard samples for transmission electron microscopy |
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