CN110184600A - The preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating - Google Patents
The preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating Download PDFInfo
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- CN110184600A CN110184600A CN201910536706.2A CN201910536706A CN110184600A CN 110184600 A CN110184600 A CN 110184600A CN 201910536706 A CN201910536706 A CN 201910536706A CN 110184600 A CN110184600 A CN 110184600A
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- oxidation resistant
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
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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
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- Mechanical Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laser Beam Processing (AREA)
Abstract
The invention discloses a kind of preparation methods of titanium alloy surface low stress high-temperature oxidation resistant coating, it is to be coated with Al/Ti/TiBCN coating material in titanium alloy surface and laser scanning cladding obtains high-temperature oxidation resistant coating, laser scanning handles to obtain remelting high-temperature oxidation resistant coating again, to refine coating structure, uniform surface residual stress is obtained；Then diffusion in vacuum heat treatment is carried out to remelting high-temperature oxidation resistant coating and HCPEB secondary remelting is handled, reduce coating internal stress, obtain low stress high-temperature oxidation resistant Al/Ti/TiBCN composite coating.
Description
Technical field
The present invention relates to a kind of preparation method of high-temperature oxidation resistant coating, more particularly to one kind based on laser melting coating and
The method that HCPEB complex technique prepares low stress high-temperature oxidation resistant coating in titanium alloy surface.
Background technique
Titanium alloy material have high specific strength, excellent corrosion stability and good mechanical behavior under high temperature, be aerospace,
The preferred structure and function material of the industries such as weapons, chemical industry, medical treatment.Wherein, mainly to mitigate knot in aerospace industry
Structure quality improves thrust ratio.
However, under the high temperature conditions, the oxidation film that titanium alloy surface is formed is mainly with porous TiO2Based on, it cannot be to oxygen
Intrusion, which is formed, effectively to be hindered；In addition, titanium alloy can burn under certain environment temperature, pressure and air velocity, such as fire
The titanium flame spread rates occurred on gas eddy turbine quickly, from burning start and ending only 4~20s.For this purpose, both at home and abroad actively
Carry out the research of titanium alloy high-temperature guard technology, changes the oxidation row of titanium alloy surface by alloying component and institutional framework control
For.Wherein, laser melting and coating technique is a kind of effective means that can obtain best mechanical property and surfacecti proteon simultaneously.
The laser melting and coating technique process for modifying surface novel as one kind, transient heating temperature height fast with heating speed,
Cooling velocity is fast, cladding composition of layer small to workpiece heat affecting and dilution are controllable, cladding layer and substrate metallurgical bonding intensity height etc.
Advantage.But under optimal processing parameter, more stress is still had in the high-temperature oxidation resistant coating of laser melting coating preparation, causes to apply
Layer loose and porous inner surface, reduces the high-temperature service performance of coating.
Summary of the invention
The purpose of the present invention is insufficient for oxidation resistance under the conditions of titanium alloy high-temperature, laser cladding coating internal stress compared with
More problems provides a kind of preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating.
The preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating of the present invention includes what following sequence carried out
Treatment process:
1) it, is coated with Al/Ti/TiBCN coating material in titanium alloy surface, with the laser power of 600~1400W to the coating material
Material carries out laser scanning cladding, obtains high-temperature oxidation resistant coating；
2) high-temperature oxidation resistant coating, is scanned again with the laser of step 1) laser power 50~85%, the high-temperature oxidation resistant is applied
Layer carries out laser remolten processing, obtains remelting high-temperature oxidation resistant coating；
3) diffusion in vacuum heat treatment, is carried out to the remelting high-temperature oxidation resistant coating；
4) secondary remelting processing, is carried out to remelting high-temperature oxidation resistant coating surface using HCPEB technology, it is anti-to obtain low stress high temperature
Aoxidize Al/Ti/TiBCN composite coating.
Wherein, the Al/Ti/TiBCN coating material is by the high-purity Al powder of 3~10wt%, 10~40wt%Ti powder and 50
~80wt%TiBCN powder combination drying obtains.
In turn, it is preferable to use the raw materials of 80~150 mesh for high-purity Al powder, Ti powder and the TiBCN powder.
Further, it is laser power 600 that laser scanning cladding of the invention, which prepares high-temperature oxidation resistant coating process conditions,
~1400W, spot diameter 4mm, protection air-flow 5~15L/min of amount, 3~9mm/s of laser scanning speed, scanning overlapping rate 30~
50%。
Further, the present invention is to be coated with the Al/Ti/TiBCN coating material by coaxial carrier gas dust feeder
In titanium alloy surface.
Preferably, the high-temperature oxidation resistant coating that the titanium alloy surface is formed with a thickness of 3~5mm.
In turn, the present invention is when carrying out laser remolten processing to the high-temperature oxidation resistant coating, first using sand paper to high temperature
Antioxidant coating surface is handled, its roughness is made to reach 5~20Ra.
Specifically, diffusion in vacuum heat treatment condition of the present invention is in vacuum degree 1 × 10-3~1 × 10-1Pa, temperature
Diffusion in vacuum is heat-treated 5~7h in 600~900 DEG C of environment.
In turn, the process conditions of HCPEB technology of the present invention are in vacuum degree 4 × 10-3~7 × 10-3Under Pa, with energy
Measure 10~35KeV, 3~8J/cm of energy density2Electron beam to remelting high-temperature oxidation resistant coating surface carry out bombardment processing.
Bombardment processing is carried out apart from remelting high-temperature oxidation resistant coating 8~35cm of surface preferably, the electron beam is arranged,
Bombardment number 1~100 time.
Preparation method of the present invention, which further comprises, pre-processes titanium alloy surface, including carries out to titanium alloy surface
Solvent cleaning treatment, to remove all dirts on surface, such as oxide skin, grease stain, paint and other dirts, especially surface and infiltration
Enter grease therein；And the preheating to titanium alloy.
Specifically, the preheating is that titanium alloy is placed in vacuum drying oven, is preheated to 100 DEG C, to reduce because titanium closes
Coating cracking caused by stress caused by thermal dilation difference between gold surface and coating material.
The present invention is compound using laser melting and coating technique and HCPEB technology, prepares low stress high temperature on titanium alloy substrate surface
Antioxidant coating.Wherein, laser melting and coating technique handles that prepare dense structure, surface residual stress uniform twice, with matrix knot
The high high-temperature oxidation resistant coating of intensity is closed, then after HCPEB technical treatment, forms one layer of reinforcing on laser cladding coating surface
Remelting coating effectively reduces the porosity of coating, has refined coating granule and has optimized element distributions in coating, has effectively reduced
Coating internal stress improves the high-temperature oxidation resistance of coating.
Detailed description of the invention
Fig. 1 is the surface residual stress profiles versus figure of remelting high-temperature oxidation resistant coating and high-temperature oxidation resistant coating.
Fig. 2 is the section SEM pattern comparison diagram of complex technique processing coating and high-temperature oxidation resistant coating.
Fig. 3 is the internal stress test result comparison diagram of complex technique processing coating and high-temperature oxidation resistant coating.
Fig. 4 is the pattern comparison diagram of complex technique processing coating and high-temperature oxidation resistant coating after 72h isothermal oxidation.
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For
For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Embodiment 1.
The high-purity Al powder of 80~150 purposes, Ti powder and TiBCN powder are screened out with mechanical picker respectively, according to the high-purity Al of 8wt%
The ratio of powder, 32wt% Ti powder and 60wt% TiBCN powder mixes 3h in the ball mill, by uniformly mixed powder at 100 DEG C
Lower vacuum drying 1h, natural cooling obtain coating material.
Using specification 20mm × 20mm × 15mm TC4 titanium alloy substrate as sample, by specimen surface with 100 mesh abrasive paper for metallograph
Carry out coarse grinding treatment, then cleaned with acetone, remove all dirts of specimen surface, including oxide skin, grease stain, paint and its
His dirt, it is important to specimen surface and penetrate into grease therein.It wipes only, with alcohol wipe, drying, is put into vacuum furnace,
100 DEG C are heated to as pretreating substrates, caused by reducing the stress because of caused by thermal dilation difference between substrate and coating material
Coating cracking.
Using laser melting and coating process technology, laser power 1200W, spot diameter 4mm are set, protect gas Ar throughput 15L/
Min, laser scanning speed 7mm/s scan overlapping rate 50%.Coating material is coated with by coaxial carrier gas dust feeder and is being located in advance
Substrate surface is managed, while carrying out laser melting coating, obtains the sample that cladding has high-temperature oxidation resistant coating.
With the particulate contamination on sand paper removal high-temperature oxidation resistant coating surface, Coating Surface Roughness is made to reach 10Ra.It adopts
Gas Ar gas is protected according to laser power 800W, laser scanning speed 5mm/s, spot diameter 4mm with laser melting and coating process technology
Flow 15L/min, longitudinal 25%, laterally 56.5% process conditions of scanning overlapping rate, swashs high-temperature oxidation resistant coating surface
Light re melting process, and use the surface impurity of 500 mesh fine sandpapers removal remelting high-temperature oxidation resistant coating.
It is answered with the surface residual of remelting high-temperature oxidation resistant coating on PSF-2M type X-ray residual stress test instrument measurement sample
Power carries out interpolation and fitting using MATLAB, obtains remelting high-temperature oxidation resistant coating surface residual stress shown in Fig. 1 (a) point
Butut.
The surface residual stress in kind measuring the high-temperature oxidation resistant coating without re melting process obtains Fig. 1 (b) institute
The high-temperature oxidation resistant coating surface residual stress distribution map shown.
By Fig. 1 (a) and (b), it is apparent that the surface residual stress of remelting high-temperature oxidation resistant coating is distributed phase in (a)
To smooth, and the phenomenon that (b) distribution of high temperature antioxidant coating surface residual stress is uneven, illustrate at laser remolten
Reason can make the distribution of sample coatings surface residual stress become uniform.
To make more uniformly spreading for remelting high-temperature oxidation resistant coating surface-element, sample is placed in vacuum degree 1 × 10-3Pa
Vacuum heat treatment furnace in, be warming up to 660 DEG C with the heating rate of 5 DEG C/min, diffusion in vacuum is heat-treated 5h.
HCPEB technology is finally used, process conditions are set are as follows: vacuum degree 5 × 10-3Pa, beam energy 20KeV, energy
Density 6J/cm2, operating distance 25cm bombards number 60 times, at remelting high-temperature oxidation resistant coating surface progress secondary remelting
Reason, the final secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating for obtaining low stress.
(a) and (b) is the secondary remelting high-temperature oxidation resistant Al/Ti/ handled by above-mentioned complex technique respectively in Fig. 2
The section SEM shape appearance figure of TiBCN composite coating and the high-temperature oxidation resistant coating without complex technique processing.Comparison discovery, (a) warp
After crossing laser re melting process and the processing of HCPEB technology secondary remelting, coating surface is smooth, fine and close, and crystal grain obviously refines.
And then YJ-31 static resistance deformeter is used, it is remnants with semiconductor silicon (sensitive grid length 7mm, 11/ DEG C of microstrain)
Ess-strain piece, circuit use full-bridge connection, with the internal stress size of ohmmeter measurement coating, and record data.
Fig. 3 gives secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating and the interior of high-temperature oxidation resistant coating is answered
Power test result comparison diagram.As a result, it has been found that the internal stress of complex technique processing coating is significantly lower than high-temperature oxidation resistant coating.
Secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating sample and high-temperature oxidation resistant coating sample are put in
In 1100 DEG C of heating furnaces, after isothermal oxidation 72h, the oxidation SEM shape appearance figure of coating cross sections is observed again.
Fig. 4 (a) and (b) are respectively that secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating and high-temperature oxidation resistant apply
The 72h isothermal oxidation pattern of layer., it is apparent that the oxidation film of complex technique processing coating is fine and close, coating inoxidizability
It is better than high-temperature oxidation resistant coating.
Embodiment 2.
The high-purity Al powder of 80~150 purposes, Ti powder and TiBCN powder are screened out with mechanical picker respectively, according to the high-purity Al of 5wt%
The ratio of powder, 25wt% Ti powder and 70wt% TiBCN powder mixes 3h in the ball mill, by uniformly mixed powder at 100 DEG C
Lower vacuum drying 1h, natural cooling obtain coating material.
The TC4 titanium alloy substrate surface (20mm × 20mm × 15mm) is subjected to coarse grinding treatment with 100 mesh abrasive paper for metallograph, then is used
Acetone is cleaned, and is wiped only, with alcohol wipe, drying, is put into vacuum furnace, is heated to 100 DEG C as pretreating substrates.
Using laser melting and coating process technology, laser power 1000W, spot diameter 4mm are set, protect gas Ar throughput 15L/
Min, laser scanning speed 5mm/s scan overlapping rate 40%.Coating material is coated with by coaxial carrier gas dust feeder and is being located in advance
Substrate surface is managed, while carrying out laser melting coating, obtains the sample that cladding has high-temperature oxidation resistant coating.
With the particulate contamination on sand paper removal high-temperature oxidation resistant coating surface, Coating Surface Roughness is made to reach 10Ra.It adopts
Gas Ar gas is protected according to laser power 600W, laser scanning speed 4mm/s, spot diameter 4mm with laser melting and coating process technology
Flow 15L/min, longitudinal 25%, laterally 56.5% process conditions of scanning overlapping rate, swashs high-temperature oxidation resistant coating surface
Light re melting process, and use the surface impurity of 500 mesh fine sandpapers removal remelting high-temperature oxidation resistant coating.
To keep coating surface Elemental redistribution uniform, sample is placed in vacuum degree 1 × 10-2In the vacuum heat treatment furnace of Pa, with 5
DEG C/heating rate of min is warming up to 660 DEG C, diffusion in vacuum is heat-treated 4h.
HCPEB technology is finally used, process conditions are set are as follows: vacuum degree 6 × 10-3Pa, beam energy 30KeV, energy
Density 5J/cm2, operating distance 20cm bombards number 40 times, at remelting high-temperature oxidation resistant coating surface progress secondary remelting
Reason, the final secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating for obtaining low stress.
Sample is tested according to 1 method of embodiment, as the result is shown compared with high-temperature oxidation resistant coating, at complex technique
Reason coating surface residual stress distribution is more uniform, and coating internal stress is smaller, after coating is oxidation-treated, dense structure and crystal grain
Tiny, antioxygenic property is excellent.
Embodiment 3.
The high-purity Al powder of 80~150 purposes, Ti powder and TiBCN powder are screened out with mechanical picker respectively, according to the high-purity Al of 3wt%
The ratio of powder, 17wt% Ti powder and 80wt% TiBCN powder mixes 3h in the ball mill, by uniformly mixed powder at 100 DEG C
Lower vacuum drying 1h, natural cooling obtain coating material.
The TC4 titanium alloy substrate surface (20mm × 20mm × 15mm) is subjected to coarse grinding treatment with 100 mesh abrasive paper for metallograph, then is used
Acetone is cleaned, and is wiped only, with alcohol wipe, drying, is put into vacuum furnace, is heated to 100 DEG C as pretreating substrates.
Using laser melting and coating process technology, laser power 800W, spot diameter 4mm are set, protect gas Ar throughput 15L/
Min, laser scanning speed 3mm/s scan overlapping rate 30%.Coating material is coated with by coaxial carrier gas dust feeder and is being located in advance
Substrate surface is managed, while carrying out laser melting coating, obtains the sample that cladding has high-temperature oxidation resistant coating.
With the particulate contamination on sand paper removal high-temperature oxidation resistant coating surface, Coating Surface Roughness is made to reach 10Ra.It adopts
Gas Ar gas is protected according to laser power 400W, laser scanning speed 3mm/s, spot diameter 4mm with laser melting and coating process technology
Flow 15L/min, longitudinal 25%, laterally 56.5% process conditions of scanning overlapping rate, swashs high-temperature oxidation resistant coating surface
Light re melting process, and use the surface impurity of 500 mesh fine sandpapers removal remelting high-temperature oxidation resistant coating.
To keep coating surface Elemental redistribution uniform, sample is placed in vacuum degree 1 × 10-1In the vacuum heat treatment furnace of Pa, with 5
DEG C/heating rate of min is warming up to 660 DEG C, diffusion in vacuum is heat-treated 7h.
HCPEB technology is finally used, process conditions are set are as follows: vacuum degree 7 × 10-3Pa, beam energy 35KeV, energy
Density 8J/cm2, operating distance 35cm bombards number 100 times, at remelting high-temperature oxidation resistant coating surface progress secondary remelting
Reason, the final secondary remelting high-temperature oxidation resistant Al/Ti/TiBCN composite coating for obtaining low stress.
Sample is tested according to 1 method of embodiment, as the result is shown compared with high-temperature oxidation resistant coating, at complex technique
Reason coating surface residual stress distribution is more uniform, and coating internal stress is smaller, after coating is oxidation-treated, dense structure and crystal grain
Tiny, antioxygenic property is excellent.
Claims (10)
1. a kind of preparation method of titanium alloy surface low stress high-temperature oxidation resistant coating carries out processed including following sequence
Journey:
1) it, is coated with Al/Ti/TiBCN coating material in titanium alloy surface, with the laser power of 600~1400W to the coating material
Material carries out laser scanning cladding, obtains high-temperature oxidation resistant coating；
2) high-temperature oxidation resistant coating, is scanned again with the laser of step 1) laser power 50~85%, the high-temperature oxidation resistant is applied
Layer carries out laser remolten processing, obtains remelting high-temperature oxidation resistant coating；
3) diffusion in vacuum heat treatment, is carried out to the remelting high-temperature oxidation resistant coating；
4) secondary remelting processing, is carried out to remelting high-temperature oxidation resistant coating surface using HCPEB technology, it is anti-to obtain low stress high temperature
Aoxidize Al/Ti/TiBCN composite coating.
2. preparation method according to claim 1, it is characterized in that the Al/Ti/TiBCN coating material is by 3~10wt% high
Pure Al powder, 10~40wt%Ti powder and 50~80wt%TiBCN powder combination drying obtain.
3. preparation method according to claim 1, it is characterized in that the laser scanning cladding prepares high-temperature oxidation resistant coating
Process conditions are as follows: 600~1400W of laser power, spot diameter 4mm, protection air-flow 5~15L/min of amount, laser scanning speed
3~9mm/s scans overlapping rate 30~50%.
4. preparation method according to claim 1, it is characterized in that by the Al/Ti/TiBCN coating material by coaxially carrying
Gas dust feeder is coated in titanium alloy surface.
5. the preparation method according to claim 4, it is characterized in that the high-temperature oxidation resistant coating that the titanium alloy surface is formed
With a thickness of 3~5mm.
6. preparation method according to claim 1, it is characterized in that by high-temperature oxidation resistant coating surface roughness processing
Laser remolten processing is carried out after to 5~20Ra.
7. preparation method according to claim 1, it is characterized in that the diffusion in vacuum heat treatment is in vacuum degree 1 × 10-3~1 × 10-1Diffusion in vacuum is heat-treated 5~7h in 600~900 DEG C of Pa, temperature environment.
8. preparation method according to claim 1, it is characterized in that the process conditions of the HCPEB technology are in vacuum degree 4
×10-3~7 × 10-3Under Pa, with 10~35KeV of energy, 3~8J/cm of energy density2Electron beam to remelting high-temperature oxidation resistant apply
Layer surface carries out bombardment processing.
9. preparation method according to claim 8 applies it is characterized in that the electron beam is arranged apart from remelting high-temperature oxidation resistant
8~35cm of layer surface carries out bombardment processing, bombards number 1~100 time.
10. preparation method according to claim 1, it is characterized in that the preparation method further includes carrying out to titanium alloy surface
Pretreatment, including solvent cleaning treatment is carried out to titanium alloy surface and titanium alloy is preheated to 100 DEG C.
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Citations (4)
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| JPH02185984A (en) * | 1989-01-10 | 1990-07-20 | Mazda Motor Corp | Production of wear resistant sealing member |
| CN103789713A (en) * | 2014-02-10 | 2014-05-14 | 江苏大学 | Anti-oxidation MCrAlY fine-grain protective coating material and preparation method thereof |
| CN108103455A (en) * | 2017-12-20 | 2018-06-01 | 江苏大学 | A kind of preparation method of the high-temperature protection coating with novel surface structure |
| CN109128135A (en) * | 2018-08-23 | 2019-01-04 | 江苏理工学院 | A kind of self-fluxing alloy powder and titanium alloy blade pulse laser remanufacture forming technology |
-
2019
- 2019-06-20 CN CN201910536706.2A patent/CN110184600B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02185984A (en) * | 1989-01-10 | 1990-07-20 | Mazda Motor Corp | Production of wear resistant sealing member |
| CN103789713A (en) * | 2014-02-10 | 2014-05-14 | 江苏大学 | Anti-oxidation MCrAlY fine-grain protective coating material and preparation method thereof |
| CN108103455A (en) * | 2017-12-20 | 2018-06-01 | 江苏大学 | A kind of preparation method of the high-temperature protection coating with novel surface structure |
| CN109128135A (en) * | 2018-08-23 | 2019-01-04 | 江苏理工学院 | A kind of self-fluxing alloy powder and titanium alloy blade pulse laser remanufacture forming technology |
Non-Patent Citations (1)
| Title |
|---|
| 苏科强 等: ""Ti6Al4V表面激光熔覆Ti/TiBCN复合涂层研究"", 《表面技术》 * |
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