CN105734642A - Preparing method for high-strength and large-specific-surface-area titanium black coating - Google Patents
Preparing method for high-strength and large-specific-surface-area titanium black coating Download PDFInfo
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- CN105734642A CN105734642A CN201610184361.5A CN201610184361A CN105734642A CN 105734642 A CN105734642 A CN 105734642A CN 201610184361 A CN201610184361 A CN 201610184361A CN 105734642 A CN105734642 A CN 105734642A
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/36—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases using ionised gases, e.g. ionitriding
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Abstract
The invention relates to a preparing method for a high-strength and large-specific-surface-area titanium black coating. The preparing method comprises the following steps that firstly, a titanium or titanium alloy base body is pretreated; secondly, a porous titanium dioxide coating is prepared; thirdly, sample plasma cleaning is conducted; fourthly, TiOx modification treatment is conducted; and fifthly, TiNxOy doping treatment is conducted. According to the preparing method, the large-specific-surface-area titanium black coating which is endowed with optical and electrical conduction functional characteristics and is capable of meeting the requirements for friction, strength and binding force can be obtained.
Description
Technical field
The present invention relates to field of surface technology, the preparation method particularly relating to a kind of high intensity, the black coating of bigger serface titanium.
Background technology
Black (the TiO of titaniumx, 0 < x < 2；Or TiNxOy, 0 < x < 1,0 < y < 2) and it is a kind of extraordinary material of blackness, not only there is TiO2High temperature resistant, the bioactive feature of antioxidation, electrochemically resistant burn into, and without the functional characteristics such as magnetic, high conductivity and optics, feature nontoxic, edible, have more environmental protection, edible feature；Therefore, titanium is black is widely used in the fields such as food, cosmetics, fuel cell, photovoltaic, chemical industry.
The research preparing titanium black-materials at present is concentrated mainly on powder body and two aspects of thin-film material, and concrete preparation method has: (1), more than 800 DEG C, adopts pure Ti reduction TiO2；(2) more than 650 DEG C, ammonia reduction TiO is adopted2；(3) more than 900 DEG C, hydrogen reducing TiO is adopted2、TiCl4Deng；(4) more than 1000 DEG C, the hydride reduction TiO of titanium is adopted2；(5) adopt sol-gel process by Ti ion or TiO2After mixing with itrogenous organic substance, high temperature sintering；Wherein, above-mentioned TiO2It is nanometer grade powder or the thin film adopting sol-gel process to prepare.
These methods exist clearly disadvantageous: (1) can not obtain the coating structure with some strength；If the black powder of titanium obtained is carried out secondary spraying, sintering can destroy the partial function characteristic that titanium is black；Adopt that the thin-film material mechanical strength prepared of sol-gel process is low to be combined with matrix poor, not there is the ability of friction resistant, anti-scratch；(2) high temperature process is needed, equipment requirements is high, and there is energy consumption deficiency big, inefficient；(3) technical difficulty is big, temperature, atmosphere, batch mixing uniformity, and in three parameters, the slight change of any one all may result in the change of the black composition of titanium, and then the performance of product is produced impact.
Chinese patent Authorization Notice No. CN103214032A discloses the " method of a kind of hydrogen plasma auxiliary hydrogenation low-temperature growth black titanium dioxide; it is characterized in that; described method includes: titanium dioxide is placed in closed system, evacuation makes the pressure of described closed system less than 30Pa；Pass into the mixed atmosphere of hydrogen and argon to described closed system, wherein, in described mixed atmosphere, argon and hydrogen mol ratio are (0～20): 1, and the content of argon can not be 0；Heat described titanium dioxide to 100～600 DEG C, regulate the flow of described mixed atmosphere so that the pressure in described closed system is 50～500pa；Open radio-frequency power supply and process time of specifying of described titanium dioxide to produce active hydrogen plasma, wherein utilize described radio-frequency power supply to ionize hydrogen molecule to produce active hydrogen plasma for reducing described titanium dioxide and obtaining black titanium dioxide "；Successfully reduce the preparation temperature that titanium is black；But the method is suitable only for manufacture powder body equally or thin film titanium is black, it is impossible to obtain and the coating structure that basal body binding force is good, mechanical strength is high；And this technique needs special professional equipment just can complete.
The Chinese patent Authorization Notice No. CN101177773A " preparation method of a kind of titanium surface black oxidation titanium film; by the titanium of surface cleaning or titanium alloy sample through atmospheric oxidn, anodic oxidation or differential arc oxidation; generate the thickness oxidation titanium film more than 0.01 μm at titanium or titanium alloy specimen surface; to the sample of its Surface Creation oxidation titanium film after washing, drying; be placed in vacuum environment or non-oxidizing atmosphere and carry out heat treatment, namely form the oxidation titanium film of black on titanium surface；Described vacuum environment refers to that vacuum is higher than the vacuum environment of 5Pa, and non-oxidizing atmosphere refers to inert atmosphere "；Disclose employing atmospheric oxidn, anodic oxidation or differential arc oxidation and prepare TiO on the surface of titanium2Oxide-film, is carrying out vacuum or inert gas shielding heat treatment, it is thus achieved that black oxide film；The method there is also deficiency: when (1) adopts modified layer based on atmospheric oxidn and anodic oxidation, and the intensity of coating improves limited (friction resistant of oxide layer, put scratch relatively ability), and coating is relatively thin, specific surface area is little；(2) but the essence of the method is by the Elements Diffusion between coating and matrix, namely Ti at high temperature reduces TiO2(preparation method 1 as black in aforementioned titanium)；Course of reaction carries out from matrix to coating surface, in order to improve the blackness of coating surface, obtain high performance coating, it is necessary to improves heat treatment temperature (more than 800 DEG C), extend heat treatment time, causes that efficiency is low, cost is high；On the other hand, by TiO2Being converted in the process that titanium is black, the change of crystal particle volume necessarily occurs, cause coating efflorescence, coating binding force, coating machine intensity are greatly reduced；Therefore, adopt the method can not the protection coating material of high-bond intensity and mechanical performance；And this technique is not suitable for processing the thin wall component (time is long, easily deforms) of the composites such as titanium aluminum, titanium copper；On the other hand, whole coating oxygen element gradient from the inside to the outside increases, and oxygen titanium elements ratio can not effectively control；Even if obtaining the titanium black layer of desirable oxygen titanium ratio, having there is also active layer too thin, coating entirety has functional characteristic hardly.
American documentation literature US20006093259A " COLORDEVELOPMENTMETHODOFMETALLICTITANIUMANDBLACKANDCOLOR EDTITANIUMMANUFACTUREDBYTHISMETHOD ", discloses the heated alkaline chemical solution oxidation bonding high temperature nitriding of employing and obtains black TiNxOyThe method of coating；Compared with above-mentioned patent, this is simple for process；But this technique there is also obvious deficiency: the coating that (1) obtains is relatively thin, poor mechanical property；(2) hot alkali treatment process generates substantial amounts of sodium titanate, cause that coating has the functional characteristic of titanium black-materials hardly containing substantial amounts of sodium titanate in coating；(3) and this technique need at 900 DEG C of nitrogen treatment carried out above, there is also the deficiency identical with above-mentioned patent, there is functional characteristic hardly；And the coating machine intensity of acquisition is low；(4) specific surface area of coating is little.
American documentation literature US20097491349B2 " BLACKTITANIUMOXYNITRIDE " discloses and adopts sol-gel process with titanium dioxide for raw material, through high temperature NH3Reduction, it is thus achieved that containing SiO2The method of the black thin film of titanium；This technique effectively raises mechanical strength and the stability of titanium black-materials or thin film, but there is also that little and matrix material the adhesion of above-mentioned specific surface area is little, reduction temperature is higher, is not suitable for low melting point or the deficiency such as the coating processing of thin wall component matrix surface.
Document " Ti6Al4V alloy surface differential arc oxidization and pulsed plasma nitriding meet study on the modification " (Harbin Institute of Technology's Master's thesis in 2009) discloses with ammonia for ion source, 750 DEG C-850 DEG C methods that TC4 titanium alloy (Ti6Al4V alloy) differential arc oxidation coating is carried out pulse plasma sealing pores.Adopt the method, in plasma nitrided sealing of hole process, following reaction occurs
TiO2+NH3→TiN+H2O
Therefore, the coating that prepared by this technique be mainly composed of TiO2-TiN gradient coating, even if the black coating surface obtained at a lower temperature is also the mixture of the titanium dioxide of TiN and titanium, lack of homogeneity, not there is the functional characteristic that titanium is black；On the other hand, the TiN of this Process Production mainly preferentially generates in surface micropore, encloses the micropore on surface, reduces the specific surface area of coating, is unfavorable for the functional performance of coating.
Summary of the invention
The preparation method that the technical problem to be solved is to provide a kind of high intensity, the black coating of bigger serface titanium, has optics and conducting function characteristic to obtain, and meets the black coating of bigger serface titanium of friction, intensity, adhesion demand.
For solving above-mentioned technical problem, the present invention adopts following technical proposals: a kind of high intensity, the black coating of bigger serface titanium preparation method, step is as follows:
Step one, substrate pretreated: titanium or titanium alloy-based surface are carried out oil removal treatment rinsing, drying, stand-by；
Prepared by step 2, primary coat: adopt micro-arc oxidation process to prepare porous silica titanium coating in the stand-by titanium of step one or titanium alloy-based surface, and clean, dry, make sample；
Step 3, plasma cleaning: the sample of step 2 is put into plasma heating furnace, evacuation, and pass into argon and carry out plasma clean；
Step 4, TiOxModification: passing into the mixture of hydrogen and argon in plasma heating furnace as ion source, glow plasma technology carries out low-temperature plasma doping, homogenize process to adopt periodicity, it is thus achieved that sub-titanium oxide black coating (i.e. TiOx, 1 < x < 2)；
Step 5, TiNxOyDoping treatment: the black coating of sub-titanium oxide obtained in step (4) in plasma heating furnace passes into the mixture of nitrogen and argon and carries out ionic nitriding, it is thus achieved that the black coating (TiN of N doping titaniumxOy, 0 < x < 1,0 < y < 2).
The further technical scheme of the present invention is:
In described step one, oil removal treatment can adopt in the sodium hydroxide containing 30-40g/L, the sodium carbonate of 20-30g/L and the sodium silicate mixed solution of 10-15g/L, temperature 50～70 DEG C, under well-beaten condition, cleans 10min-15min；Or adopt the organic solution ultrasonic cleaning such as acetone；
In described step 2, micro-arc oxidation electrolyte type is determined according to the instructions for use of coating；Choose without heavy metal, or the environmental protection solution without harmful element, it is 350V-550V at voltage, frequency is 200Hz-1000Hz, when dutycycle is 8%-50%, processes 20min～90min in Oxygen in Electrolytical Solutionization；Wherein, electrolyte solution is made up of the silicic acid of 5g/L-30g/L or the additive such as the main salt of phosphoric acid and the glycerol of 3ml/L-15ml/L, triethanolamine, EDTA or ethanol and water；
In described step 3, the temperature 100 DEG C-300 DEG C that plasma cleaning processes, voltage 400V-600V, plasma heating furnace internal gas pressure 150Pa-300Pa, the process time is 10min-20min；
In described step 4, doping treatment will heat up to 200 DEG C-500 DEG C, voltage 500V-1000V, carries out periodically modified；Wherein, in each cycle the first stage pass into argon and hydrogen or in each cycle the first stage pass into argon and nitrogen, and maintain between 100Pa-600Pa, be modified processing 30min-60min；Second stage passes into argon, and is evacuated to below 50Pa, passes into argon insulation 10min-30min；The circulation of whole processing procedure carries out 10-50 cycle；
In described step 5, before passing into nitrogen and ar mixture, it is evacuated to below 50Pa, and maintains 100Pa-600Pa, nitrogen treatment 2h-5h.
Effect and the benefit of the present invention include:
(1) coating has the conduction of excellence, photocatalysis performance
The black coating of titanium of the present invention is mainly composed of sub-titanium oxide or titanium oxynitrides, has conduction, light-catalysed functional characteristic；And the microstructure of this coating surface is porous, coarse shape, has bigger specific surface area；Therefore, this compares the coating adopting the technique such as chemical oxidation-reduction and sputter coating to prepare, and this coating has better functional characteristic；
(2) mechanical strength of coating is high, and adhesion is strong
The follow-up modifying process of the present invention carries out at a lower temperature, and periodically carries out being effectively controlled the speed of doping, releasing the volumetric stress that doping causes, promoted the effective integration of matrix, coating and coat inside element, it is to avoid the efflorescence of coating；Therefore, coating remains bond strength and the mechanical performance of micro-arc oxidation process coating, has better wear-resisting, corrosion resisting property；
(3) this coating can be used for the non-stick pan process of cooker
Coating prepared by the present invention is safe and healthy, edible, meets the demand of diet；Coating has extraordinary lipophile, and loose structure can obtain the not viscous effect of physics.
Accompanying drawing explanation
Accompanying drawing 1 is the embodiment of the present invention one surface SEM pattern.
Accompanying drawing 2 is the embodiment of the present invention one surface EDS collection of illustrative plates.
Accompanying drawing 3 is the embodiment of the present invention one XRD figure spectrum.
Accompanying drawing 4 is pattern and the EDS collection of illustrative plates of the embodiment of the present invention two sample.
Accompanying drawing 5 is pattern and the EDS collection of illustrative plates of the embodiment of the present invention three sample.
Accompanying drawing 6 is pattern and the EDS collection of illustrative plates of the embodiment of the present invention four sample.
Accompanying drawing 7 is pattern and the EDS collection of illustrative plates of the embodiment of the present invention five sample.
Accompanying drawing 8 is pattern and the EDS collection of illustrative plates of the embodiment of the present invention six sample.
Detailed description of the invention
Embodiment 1
Shown in Fig. 1-Fig. 3, a kind of high intensity, the black coating of bigger serface titanium preparation method, adopt 25 × 250 × 1mm TC4 alloy lath be sample, its surface TiOxThe processing technology of the black coating of titanium is as follows:
Step one, substrate pretreated: in the sodium silicate mixed solution of sodium hydroxide containing 40g/L, the sodium carbonate of 30g/L and 15g/L, temperature 70 C, and under well-beaten condition, clean 10min；
Prepared by step 2, primary coat: constant voltage 550V, frequency are 200Hz, dutycycle processes 20min in Oxygen in Electrolytical Solutionization when being 30%；Wherein, electrolyte solution is made up of the G & W of the sodium silicate of 30g/L, 10ml/L；
Step 3, plasma cleaning: be evacuated to 50Pa, pass into argon 150Pa, is warming up to 300 DEG C, voltage 500V, and the process time is 15min；
Step 4, TiOxModification: be warming up to 500 DEG C, carries out periodically modification；Wherein the monocyclic first stage passes into argon and hydrogen mixture, maintains 120Pa, voltage 500V, processes 30min；Monocycle second stage, is evacuated to 50Pa, passes into argon, is incubated 10min；Periodic cycle processes 10 times, it is thus achieved that TiOxThe black coating of titanium.
Embodiment 2
Shown in Figure 4, a kind of high intensity, the black coating of bigger serface titanium preparation method, adopt 25 × 250 × 1mm TC4 alloy lath be sample, the processing technology of its black coating of surface TiO x titanium is as follows:
Step one, substrate pretreated: in the sodium silicate mixed solution of sodium hydroxide containing 30g/L, the sodium carbonate of 20g/L and 10g/L, temperature 50 C, and under well-beaten condition, clean 15min；
Prepared by step 2, primary coat: constant voltage 350V, frequency are 500Hz, dutycycle when being 50%, process 90min in Oxygen in Electrolytical Solutionization；Wherein, electrolyte solution is made up of 5g/L Polymeric sodium metaphosphate., 3ml/L triethanolamine and deionized water；
Step 3, plasma cleaning: be evacuated to 50Pa, pass into argon 300Pa, is warming up to 100 DEG C, voltage 400V, and the process time is 20min；
Step 4, TiOxModification: be warming up to 200 DEG C, carries out periodically modification；Wherein the monocyclic first stage passes into argon and hydrogen mixture, maintains 600Pa, voltage 1000V, processes 60min；Monocycle second stage, is evacuated to 50Pa, passes into argon, is incubated 30min；Periodic cycle processes 50 times, it is thus achieved that TiOxThe black coating of titanium.
Embodiment 3
Shown in Figure 5, a kind of high intensity, the black coating of bigger serface titanium preparation method, adopt 25 × 250 × 1mm TC4 alloy lath be sample, the processing technology of its black coating of surface TiO x titanium is as follows:
Step one, substrate pretreated: in acetone soln, adopt ultrasonic cleaning 10min；
Porous structure layer: constant voltage 350V inside step 2, prefabricated pot, frequency are 1000Hz, dutycycle when being 8%, process 60min in Oxygen in Electrolytical Solutionization；Wherein, electrolyte solution is made up of 15g/L sodium phosphate, the EDTA (ethylenediaminetetraacetic acid) of 10ml/Ld and deionized water；
Step 3, plasma cleaning: be evacuated to 50Pa, pass into argon 200Pa, is warming up to 250 DEG C, voltage 500V, and the process time is 10min；
Step 4, TiOxModification: be warming up to 350 DEG C, carries out periodically modification；Wherein the monocyclic first stage passes into argon and hydrogen mixture, maintains 260Pa, voltage 500V, processes 40min；Monocycle second stage, is evacuated to 50Pa, passes into argon, is incubated 20min；Periodic cycle processes 30 times, it is thus achieved that TiOxThe black coating of titanium.
Embodiment 4
Shown in Figure 6, a kind of high intensity, the black coating of bigger serface titanium preparation method, the TC4 alloy lath adopting 25 × 250 × 1mm is sample, and the processing technology of its surface black coating of TiNxOy titanium is as follows: concrete processing technology is made up of five steps, and step one is identical with embodiment one to step 4；
Increase step 5, TiNxOyDoping treatment: be again evacuated to below 50Pa, passes into the mixture of nitrogen and argon, and maintains 300Pa, nitrogen treatment 2h, it is thus achieved that TiNxOyThe black coating of titanium.
Embodiment 5
Shown in Figure 7, a kind of high intensity, the black coating of bigger serface titanium preparation method, adopt 25 × 250 × 1mm TC4 alloy lath be sample, its surface TiNxOyThe processing technology of the black coating of titanium is as follows: concrete processing technology is made up of five steps, and step one is identical with embodiment two to step 4；
Increase step 5, TiNxOyDoping treatment: be again evacuated to below 50Pa, passes into the mixture of nitrogen and argon, and maintains 600Pa, nitrogen treatment 5h, it is thus achieved that TiNxOyThe black coating of titanium.
Embodiment 6
Shown in Figure 8, a kind of high intensity, the black coating of bigger serface titanium preparation method, adopt 25 × 250 × 1mm TC4 alloy lath be sample, its surface TiNxOyThe processing technology of the black coating of titanium is as follows: concrete processing technology is made up of five steps, and step one is identical with embodiment three to step 4；
Increase step 5, TiNxOyDoping treatment: be again evacuated to below 50Pa, passes into the mixture of nitrogen and argon, and maintains 120Pa, nitrogen treatment 3.5h, it is thus achieved that TiNxOyThe black coating of titanium.
As mentioned above; a kind of high intensity of the present invention, the black coating of bigger serface titanium preparation method; described embodiment and figure; the simply good implementation result of the present invention; it is not be confined to the present invention; every person approximate with the structure of the present invention, feature etc., identical, all should belong to the scope of protection of the invention.
Claims (2)
1. the preparation method of a high intensity, the black coating of bigger serface titanium, it is characterised in that step is as follows:
Step one, substrate pretreated: titanium or titanium alloy-based surface are carried out oil removal treatment rinsing, drying, stand-by；
Prepared by step 2, primary coat: adopt micro-arc oxidation process to prepare porous silica titanium coating in the stand-by titanium of step one or titanium alloy-based surface, and clean, dry, make sample；
Step 3, plasma cleaning: the sample of step 2 is put into plasma heating furnace, evacuation, and pass into argon and carry out plasma clean；
Step 4, TiOxModification: passing into the hydrogen mixture with argon in plasma heating furnace as ion source, glow plasma technology carries out low-temperature plasma doping, homogenize process to adopt periodicity, it is thus achieved that sub-titanium oxide black coating (i.e. TiOx, 1 < x < 2)；
Step 5, TiNxOyDoping treatment: the black coating of sub-titanium oxide obtained in step (4) in plasma heating furnace passes into the mixture of nitrogen and argon and carries out ionic nitriding, it is thus achieved that the black coating (TiN of N doping titaniumxOy, 0 < x < 1,0 < y < 2).
2. the preparation method of a kind of high intensity according to claim 1, the black coating of bigger serface titanium, it is characterised in that:
In described step one, oil removal treatment can adopt in the sodium hydroxide containing 30-40g/L, the sodium carbonate of 20-30g/L and the sodium silicate mixed solution of 10-15g/L, temperature 50～70 DEG C, under well-beaten condition, cleans 10min-15min；Or adopt the organic solution ultrasonic cleaning such as acetone；
In described step 2, micro-arc oxidation electrolyte type is determined according to the instructions for use of coating；Choose without heavy metal, or the environmental protection solution without harmful element, it is 350V-550V at voltage, frequency is 200Hz-1000Hz, when dutycycle is 8%-50%, processes 20min～90min in Oxygen in Electrolytical Solutionization；Wherein, electrolyte solution is made up of the silicic acid of 5g/L-30g/L or the additive such as the main salt of phosphoric acid and the glycerol of 3ml/L-15ml/L, triethanolamine, EDTA or ethanol and water；
In described step 3, the temperature 100 DEG C-300 DEG C that plasma cleaning processes, voltage 400V-600V, plasma heating furnace internal gas pressure 150Pa-300Pa, the process time is 10min-20min；
In described step 4, doping treatment will heat up to 200 DEG C-500 DEG C, voltage 500V-1000V, carries out periodically modified；Wherein, in each cycle the first stage pass into argon and hydrogen or in each cycle the first stage pass into argon and nitrogen, and maintain between 100Pa-600Pa, be modified processing 30min-60min；Second stage passes into argon, and is evacuated to below 50Pa, passes into argon insulation 10min-30min；The circulation of whole processing procedure carries out 10-50 cycle；
In described step 5, before passing into nitrogen and ar mixture, it is evacuated to below 50Pa, and maintains 100Pa-600Pa, nitrogen treatment 2h-5h.
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| CN110180034A (en) * | 2019-05-29 | 2019-08-30 | 中国科学院上海硅酸盐研究所 | A kind of reduction-state titanium oxide coating and preparation method and application |
| JP2019157273A (en) * | 2018-03-12 | 2019-09-19 | 三菱マテリアル株式会社 | Titanium base material, manufacturing method thereof, electrode for water electrolysis, and water electrolysis device |
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| CN110655151A (en) * | 2019-10-09 | 2020-01-07 | 江西省科学院应用物理研究所 | Preparation method of titanium-based titanium suboxide porous electrode |
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| 李伟: "i6Al4V 合金表面微弧氧化及脉冲等离子体渗氮复合改性研究", 《哈尔滨工业大学硕士学位论文》 * |
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