CN107937874A - A kind of method for preparing Pt Al high-temperature protection coatings on niobium alloy surface - Google Patents
A kind of method for preparing Pt Al high-temperature protection coatings on niobium alloy surface Download PDFInfo
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- CN107937874A CN107937874A CN201710961019.6A CN201710961019A CN107937874A CN 107937874 A CN107937874 A CN 107937874A CN 201710961019 A CN201710961019 A CN 201710961019A CN 107937874 A CN107937874 A CN 107937874A
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
- C23C10/48—Aluminising
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/46—Sputtering by ion beam produced by an external ion source
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- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a kind of method for preparing Pt Al high-temperature protection coatings on niobium alloy surface, comprise the following steps：（1）Niobium alloy matrix surface is pre-processed, uses deionized water rinsing after being cleaned by ultrasonic totally with acetone again, drying is spare；（2）Will be through step（1）The niobium alloy matrix handled well is put into the preparation of Pt layers of progress in ion sputtering instrument；（3）Will be through step（2）Pt Al high-temperature protection coatings are made on niobium alloy surface after what is be prepared carry out embedding aluminizing containing Pt layers of niobium alloy matrix.Al constituent contents are 60~70wt% in the Pt Al high-temperature protection coatings, and Pt constituent contents are 2~8wt%, and Nb constituent contents are 20~30wt%.Pt Al high-temperature protection coatings prepared by the present invention are continuous fine and close smooth, are in metallurgical binding with niobium alloy matrix, and bond strength is high and preparation process is vacuum ion sputtering method, different from traditional electro-plating method, have the advantages that easy to operate, saving energy consumption.
Description
Technical field
It is more particularly to a kind of to prepare Pt-Al high temperature on niobium alloy surface the present invention relates to high temperature coating protection technology field
The method of protective coating.
Background technology
With the development of high thrust-weight ratio aero-engine, the use environment of its turbo blade is more harsh, this is to blade material
The performance of material proposes the requirement of higher.The fusing point of niobium is high, and medium density, high temperature specific strength is big, has excellent high-temperature mechanics
Performance and processing performance, are considered one of important candidate material of high-temperature structural material.But the inoxidizability of niobium is poor, at 600 DEG C
" pest " oxidation is formed, strongly limit its application.According to research reports, on niobium alloy surface, coating has protective to root
Coating, niobic alloy high temperature antioxidation can be effectively improved, and its mechanical behavior under high temperature can be taken into account, and coating Protection Code is easy
Realize, significant effect, therefore be widely used.
Coat of aluminide is to apply most common coating at present, relies primarily on the oxygen that aluminium under high temperature combines to form densification with oxygen
Change the diffusion that aluminium film stops oxygen, so as to improve the inoxidizability of material.But the single mechanical behavior under high temperature for being put into coat of aluminide
Difference, heat shock resistance external force is weak, can cause coating failure under stand under load effect.Platinum modified aluminide coating has been found to improve
Al2O3The combination power of film and matrix, and strengthen the structure stability of coating, suppress element to external diffusion.Platinum can improve oxidation
Film selectively produces, and new oxide layer can be comparatively fast generated after oxide layer deterioration, that is, is provided with self-healing function.Platinum element
Doping, can reduce the internal stress of oxide-film to a certain extent, improve the adhesiveness of oxide-film.In addition the presence of platinum also reduces
The enrichment of S elements, so that metal layer loses the possibility for producing hole with oxide interface.Another to have been reported that display, platinum can be with
The speed that matrix element is spread to coating is reduced, and then reduces the generation of detrimental oxide.Multiple achievements in research show, relatively
For other modified aluminide coatings, the high-temperature oxidation resistance of platinum modified aluminide coating will be much better than other coatings.Phase
Close the document of application such as：（1）Chinese invention patent, a kind of single-phase platinum modified aluminide coating and its preparation process, application number
20141061091.1；（2）Chinese invention patent, a kind of preparation method of nano platinum oxidation coating for high temperature alloy, application
Numbers 200810058933.0；（3）Chinese invention patent, a kind of protective coating for single crystal super alloy and preparation method thereof,
Application number 201310509194.3 etc..
The preparation method of platinum layer mainly has：（1）The compound platinum of metallurgical processing, is prepared using modes such as rolling, drawing, extruding
Compound platinum.Material cladding interface bond strength height, the platinum layer of this method preparation are continuously non-porous, and thickness is controllable, but for preparing
Less than 10 μm of platinum layer is difficult, is more difficult to process for complex-shaped workpiece.（2）Electro-plating method prepares platinum layer, and utilization is additional
Metal ion in electroplate liquid is reduced and is deposited as platinum by electric current on cathode (workpiece), including Molten Salt Electroplating and aqueous solution electricity
Plate two ways.Fused salt platinum plating complex process operating environment is poor, costly；Aqueous solution plating is currently used acquisition platinum layer
More economical practical method, shortcoming is that required electroplate liquid formulation is complicated, produces more industrial wastewater.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of less energy consumption, easy to operate, obtains coating company
Continuous densification, is well combined with matrix, can effectively improve the side of the Pt-Al high-temperature protection coatings of the high-temperature oxidation resistance of niobium alloy
Method.
The technical scheme is that：A kind of method for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, including with
Lower step：
（1）Niobium alloy matrix surface is pre-processed, successively using 240#, 400#, 600#, 800#, 1000# and 1500# sand
Paper polishing is bright and clean, uses deionized water rinsing after being cleaned by ultrasonic totally with acetone again, and drying is spare；
（2）Will be through step（1）The niobium alloy matrix handled well is put into the preparation of Pt layers of progress in ion sputtering instrument；Target is pt
Target, target to niobium alloy substrate of substrate stage 20~30mm of distance, evacuation rate is 20~25I/min, sputtering vacuum for 5~
15Pa, electric current are 45~48mA, and sputtering time is 2~5min, and the Pt that thickness is 8~12nm is made in niobium alloy matrix surface
Layer；
（3）Will be through step（2）What is be prepared carries out embedding aluminizing containing Pt layers of niobium alloy matrix；First containing Pt layers
Niobium alloy matrix is sealed into the crucible full of aluminizing medium, and then the crucible is put into vacuum tube furnace, is vacuumized and is heated up
To 300~350 DEG C of 1~2h of insulation, it is further continued for being warming up to 900~1000 DEG C, keeps the temperature and be cooled to room with vacuum tube furnace after 4~6h
Temperature, Pt-Al high-temperature protection coatings are made on niobium alloy surface.
Further, the step（1）In Pt targets purity be 99.9~99.999%.
Further, the step（3）In aluminizing medium component be by weight percentage 5~12% Al powder, 1~5%
NaF powder, surplus Al2O3Powder, three of the above powder through mixing and ball milling 1~5 it is small when be made.
Further, the thickness of the Pt-Al high-temperature protection coatings is 60~75 μm, Al in Pt-Al high-temperature protection coatings
Constituent content is 60~70wt%, and Pt constituent contents are 2~8wt%, and Nb constituent contents are 20~30wt%.
The beneficial effects of the invention are as follows：
1st, the Pt layer preparation processes that the present invention uses, different from traditional electro-plating method, have operation for vacuum ion sputtering method
Simplicity, save the advantages of energy consumption, highly shortened Pt layers of preparation time, and ion sputtering instrument has ultralow discharge voltage,
Electric current is without by sample, increasing extent of temperature is small, weakens sample damage.
2nd, Pt-Al high-temperature protection coatings prepared by the present invention are continuous fine and close smooth, are in metallurgical binding with niobium alloy matrix, knot
It is high to close intensity.
3rd, the Pt-Al high-temperature protection coatings that the present invention obtains are compared with single coat of aluminide, at the same temperature
Oxidation resistance is greatly improved.
Brief description of the drawings
Fig. 1 is Pt-Al high-temperature protection coating Cross Section Morphology figures prepared by the embodiment of the present invention 1.
Fig. 2 is the high-temperature oxydation weightening pair of Pt-Al high-temperature protection coatings prepared by the embodiment of the present invention 1 and single calorized coating
Than figure.
Fig. 3 is the XRD spectrum before and after Pt-Al high-temperature protection coatings oxidation prepared by the embodiment of the present invention 1.
Fig. 4 is that Pt-Al high-temperature protection coatings prepared by the embodiment of the present invention 1 aoxidize rear surface shape appearance figure.
Fig. 5 is Cross Section Morphology figure after Pt-Al high-temperature protection coatings oxidation prepared by the embodiment of the present invention 1.
Reference numeral：1- Electroless Plating Ni protective layers, 2-Pt-Al high-temperature protection coatings, 3-C103 niobium alloy matrixes, 4- oxidations
Product.
Embodiment
Embodiment 1
A kind of method for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, comprises the following steps：
1st, matrix selection C103 niobium alloys, its chemical composition are as shown in the table
| Component | Hf | Ti | Zr | W | Ta | Nb |
| Content wt（%） | 10.0 | 1.30 | 0.34 | 0.31 | 0.30 | Bal. |
Niobium alloy matrix surface is pre-processed, is beaten successively using 240#, 400#, 600#, 800#, 1000# and 1500# sand paper
Polish it is clean, with acetone be cleaned by ultrasonic it is clean after use deionized water rinsing again, dry up spare；
The 2nd, the niobium alloy matrix handled well through step 1 is put into the preparation of Pt layers of progress in MSP-1S type ion sputtering instruments；Target
For Pt targets, its purity is 99.9~99.999%；Target to niobium alloy substrate of substrate stage distance 25mm, evacuation rate 20I/min,
Sputtering vacuum is 10Pa, electric current 47mA, sputtering time 2min, and it is 8~12nm that thickness, which is made, in niobium alloy matrix surface
Pt layers；
3rd, by what is be prepared through step 2 embedding aluminizing is carried out containing Pt layers of niobium alloy matrix；First the niobium containing Pt layers
Alloy substrate is sealed into the crucible full of aluminizing medium, and the aluminizing medium component is 10% Al powder by weight percentage, and 3%
NaF powder, surplus Al2O3Powder, three of the above powder through mixing and ball milling 2 it is small when be made；Then the crucible is put into vacuum tube
In formula stove, vacuumize and be warming up to 300 DEG C of insulation 1h, be further continued for being warming up to 940 DEG C, be cooled to after keeping the temperature 4h with vacuum tube furnace
Room temperature, Pt-Al high-temperature protection coatings are made on niobium alloy surface.
Embodiment 2
1st, matrix selection C103 niobium alloys, its chemical composition are as shown in the table
| Component | Hf | Ti | Zr | W | Ta | Nb |
| Content wt（%） | 10.0 | 1.30 | 0.34 | 0.31 | 0.30 | Bal. |
Niobium alloy matrix surface is pre-processed, is beaten successively using 240#, 400#, 600#, 800#, 1000# and 1500# sand paper
Polish it is clean, with acetone be cleaned by ultrasonic it is clean after use deionized water rinsing again, dry up spare；
The 2nd, the niobium alloy matrix handled well through step 1 is put into the preparation of Pt layers of progress in MSP-1S type ion sputtering instruments；Target
For Pt targets, its purity is 99.9~99.999%；Target to niobium alloy substrate of substrate stage distance 25mm, evacuation rate 20I/min,
Sputtering vacuum is 10Pa, electric current 47mA, sputtering time 2min, and it is 8~12nm that thickness, which is made, in niobium alloy matrix surface
Pt layers；
3rd, by what is be prepared through step 2 embedding aluminizing is carried out containing Pt layers of niobium alloy matrix；First the niobium containing Pt layers
Alloy substrate is sealed into the crucible full of aluminizing medium, and the aluminizing medium component is 10% Al powder by weight percentage, and 5%
NaF powder, surplus Al2O3Powder, three of the above powder through mixing and ball milling 2 it is small when be made；Then the crucible is put into vacuum tube
In formula stove, vacuumize and be warming up to 300 DEG C of insulation 1h, be further continued for being warming up to 940 DEG C, be cooled to after keeping the temperature 4h with vacuum tube furnace
Room temperature, Pt-Al high-temperature protection coatings are made on niobium alloy surface.
Embodiment 3
1st, matrix selection C103 niobium alloys, its chemical composition are as shown in the table
| Component | Hf | Ti | Zr | W | Ta | Nb |
| Content wt（%） | 10.0 | 1.30 | 0.34 | 0.31 | 0.30 | Bal. |
Niobium alloy matrix surface is pre-processed, is beaten successively using 240#, 400#, 600#, 800#, 1000# and 1500# sand paper
Polish it is clean, with acetone be cleaned by ultrasonic it is clean after use deionized water rinsing again, dry up spare；
The 2nd, the niobium alloy matrix handled well through step 1 is put into the preparation of Pt layers of progress in MSP-1S type ion sputtering instruments；Target
For Pt targets, its purity is 99.9~99.999%；Target to niobium alloy substrate of substrate stage distance 25mm, evacuation rate 20I/min,
Sputtering vacuum is 10Pa, electric current 47mA, sputtering time 2min, and it is 8~12nm that thickness, which is made, in niobium alloy matrix surface
Pt layers；
3rd, by what is be prepared through step 2 embedding aluminizing is carried out containing Pt layers of niobium alloy matrix；First the niobium containing Pt layers
Alloy substrate is sealed into the crucible full of aluminizing medium, and the aluminizing medium component is 10% Al powder by weight percentage, and 5%
NaF powder, surplus Al2O3Powder, three of the above powder through mixing and ball milling 2 it is small when be made；Then the crucible is put into vacuum tube
In formula stove, vacuumize and be warming up to 300 DEG C of insulation 1h, be further continued for being warming up to 1000 DEG C, cooled down after keeping the temperature 4h with vacuum tube furnace
To room temperature, Pt-Al high-temperature protection coatings are made on niobium alloy surface.
Using the phase structure of X-ray diffraction detection coating, scanning electron microscope is utilized（SEM）The Cross Section Morphology of coating is observed,
When preparing cross-sectional sample, in advance in sample surfaces Electroless Plating Ni layer, to protect cross-sectional sample coating morphology.
As shown in Figure 1, Pt-Al high-temperature protection coatings are continuously fine and close made from embodiment 1, combined with C103 niobium alloy matrixes
Well, the defects of flawless, hole；Detect and find through EDS, Al constituent contents are 64.96wt% in coating, and Nb contents are 22.34
Wt%, Pt content are 3.56 wt%.
Reference as a comparison, in C103 niobium alloy matrix surface list aluminide coatings, its preparation method and the difference of embodiment 1
It is：There is no the link of step 2.Pt-Al high-temperature protection coatings made from embodiment 1 and niobium alloy matrix surface list are oozed Al to apply
Layer carries out high-temperature oxydation experiment in resistance furnace respectively, and experimental temperature is 1100 DEG C, when experimental period is 100 small, respectively in reality
Before testing, 2h, 5h, 10h, 20h, 30h, 50h and 100h when weigh the quality of sample, and record.
As shown in Fig. 2, Pt-Al coatings and the growth of both coating qualities of single calorized coating are relatively put down before the first 20h of oxidation
Slow, single calorized coating starts quickly to be aoxidized after 20h, and mass-change curve slope becomes larger, and Pt-Al coatings are aoxidized before 30h
Relatively slow, the more single calorized coating of oxidation resistance after 30h is also significantly increased；In contrast, the Pt-Al that prepared by embodiment 1 is applied
Layer has C103 niobium alloy matrixes preferable high temperature protection to act on.
As shown in figure 3, Pt-Al high-temperature protection coatings are by Al made from embodiment 13Nb and PtAl2Two kinds of thing phase compositions, Pt
Layer external diffusion combines to form PtAl with Al2Phase, the Nb elements in matrix alloy are combined to external diffusion with the Al elements of surface deposition
Form Al3Nb phases.After oxidation, coating surface generation Al2O3With part Nb2O5Phase.With reference to shown in Fig. 2, compared to single calorized coating, Pt
The presence of element causes Al elements to be easy to external diffusion to a certain extent, promotes Al2O3The formation of film layer, and improve Al2O3Film from
Healing ability, improves coating oxidation resistance.As oxidation carries out, PtAl2Mutually gradually use up, Al2O3Film gradually comes off,
Nb elements are combined generation Nb with O in matrix2O5Phase.
As shown in Figure 4 and Figure 5, after Pt-Al high-temperature protection coatings are oxidized made from embodiment 1, the cotton-shaped oxygen of Surface Creation
Change product, detected through EDS, O constituent contents are 35.64wt%, and Al constituent contents are 41.02 wt%, and Nb constituent contents are 8.10
Wt%, can obtain, oxidation product is Al with reference to XRD Analysis of test results in Fig. 32O3And Nb2O5.After oxidation in coating internal layer still
Fine and close and continuous, flawless and hole occur, and associativity is good.
The above description is merely a specific embodiment, but protection scope of the present invention is not limited thereto, any
The change expected without creative work or simple replacement, should all be included within the scope of the present invention.
Claims (4)
- A kind of 1. method for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, it is characterised in that comprise the following steps：（1）Niobium alloy matrix surface is pre-processed, successively using 240#, 400#, 600#, 800#, 1000# and 1500# sand Paper polishing is bright and clean, uses deionized water rinsing after being cleaned by ultrasonic totally with acetone again, and drying is spare；（2）Will be through step（1）The niobium alloy matrix handled well is put into the preparation of Pt layers of progress in ion sputtering instrument；Target is pt Target, target to niobium alloy substrate of substrate stage 20~30mm of distance, evacuation rate is 20~25I/min, sputtering vacuum for 5~ 15Pa, electric current are 45~48mA, and sputtering time is 2~5min, and the Pt that thickness is 8~12nm is made in niobium alloy matrix surface Layer；（3）Will be through step（2）What is be prepared carries out embedding aluminizing containing Pt layers of niobium alloy matrix；First containing Pt layers Niobium alloy matrix is sealed into the crucible full of aluminizing medium, and then the crucible is put into vacuum tube furnace, is vacuumized and is heated up To 300~350 DEG C of 1~2h of insulation, it is further continued for being warming up to 900~1000 DEG C, keeps the temperature and be cooled to room with vacuum tube furnace after 4~6h Temperature, Pt-Al high-temperature protection coatings are made on niobium alloy surface.
- 2. the method according to claim 1 for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, it is characterised in that： The step（1）In Pt targets purity be 99.9~99.999%.
- 3. the method according to claim 1 for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, it is characterised in that： The step（3）In aluminizing medium component by weight percentage be 5~12% Al powder, 1~5% NaF powder, surplus Al2O3 Powder, three of the above powder through mixing and ball milling 1~5 it is small when be made.
- 4. the method according to claim 1 for preparing Pt-Al high-temperature protection coatings on niobium alloy surface, it is characterised in that： The thickness of the Pt-Al high-temperature protection coatings is 60~75 μm, in Pt-Al high-temperature protection coatings Al constituent contents for 60~ 70wt%, Pt constituent content are 2~8wt%, and Nb constituent contents are 20~30wt%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108642439A (en) * | 2018-06-05 | 2018-10-12 | 合肥工业大学 | A method of preparing high-strength coating in tungsten alitizing |
| CN114807709A (en) * | 2022-04-22 | 2022-07-29 | 昆明理工大学 | Rare noble metal niobium alloy gradient material and preparation method thereof |
| CN114921691A (en) * | 2022-05-19 | 2022-08-19 | 昆明理工大学 | Niobium alloy material coating optimized based on rare and noble metals and preparation method thereof |
| CN115011924A (en) * | 2022-04-24 | 2022-09-06 | 昆明理工大学 | High-temperature oxidation resistant alloy and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108642439A (en) * | 2018-06-05 | 2018-10-12 | 合肥工业大学 | A method of preparing high-strength coating in tungsten alitizing |
| CN108642439B (en) * | 2018-06-05 | 2020-04-14 | 合肥工业大学 | Method for preparing high-strength coating on surface of metal tungsten through aluminizing |
| CN114807709A (en) * | 2022-04-22 | 2022-07-29 | 昆明理工大学 | Rare noble metal niobium alloy gradient material and preparation method thereof |
| CN114807709B (en) * | 2022-04-22 | 2023-11-10 | 昆明理工大学 | Rare noble metal niobium alloy gradient material and preparation method thereof |
| CN115011924A (en) * | 2022-04-24 | 2022-09-06 | 昆明理工大学 | High-temperature oxidation resistant alloy and preparation method and application thereof |
| CN114921691A (en) * | 2022-05-19 | 2022-08-19 | 昆明理工大学 | Niobium alloy material coating optimized based on rare and noble metals and preparation method thereof |
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| CN107937874B (en) | 2019-10-08 |
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