CN105331869A - Multi-principal element alloy and method for surface treatment of titanium alloy - Google Patents
Multi-principal element alloy and method for surface treatment of titanium alloy Download PDFInfo
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- CN105331869A CN105331869A CN201510857736.5A CN201510857736A CN105331869A CN 105331869 A CN105331869 A CN 105331869A CN 201510857736 A CN201510857736 A CN 201510857736A CN 105331869 A CN105331869 A CN 105331869A
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 66
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910001325 element alloy Inorganic materials 0.000 title abstract 6
- 238000004381 surface treatment Methods 0.000 title abstract 2
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- 238000000576 coating method Methods 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 12
- 238000005507 spraying Methods 0.000 claims abstract description 11
- 238000007750 plasma spraying Methods 0.000 claims abstract description 10
- 239000010936 titanium Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000007788 roughening Methods 0.000 claims abstract description 5
- 238000005488 sandblasting Methods 0.000 claims abstract description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 39
- 239000000956 alloy Substances 0.000 claims description 39
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 238000010309 melting process Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 12
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 abstract 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 4
- 238000000280 densification Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005468 ion implantation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
- C23C4/06—Metallic material
-
- 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
- C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
- C23C4/18—After-treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Coating By Spraying Or Casting (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Abstract
The invention discloses a multi-principal element alloy and a method for surface treatment of a titanium alloy. The multi-principal element alloy comprises, by mole, 18-30 parts of Zr, 18-30 parts of Ni, 18-30 parts of Si, 18-30 parts of Ta, 1-10 parts of Ti and 2-5 parts of CeO2. According to the method, a titanium alloy base material is cleaned and subjected to sand blasting roughening treatment, then plasma spraying equipment is used for spraying multi-principal element alloy powder on the surface of the titanium alloy base material, finally the plasma-sprayed surface is subjected to remelting treatment through a CO2 laser device, and a coating is obtained. The prepared multi-principal element alloy coating adopts characteristics of high-entropy effect, slow diffusion effect, nanophase reinforcement, super-high lattice deformation, cocktail effect and the like of the multi-principal element alloy, abrasion resistance and high temperature oxidation resistance of the titanium alloy can be remarkably improved, and titanium fire can be prevented.
Description
Technical field
The invention belongs to material surface process and intensifying technology field, be specifically related to a kind of multi-principal elements alloy and for the method to titanium alloy surface process.
Background technology
Titanium or titanium alloy has that proportion is low, specific tenacity is high, yield tensile ratio is high, the corrosion resistance by force and under the high temperature conditions advantage such as good mechanical properties, has the application increased gradually in a lot of fields.But due to titanium alloy have that frictional coefficient is high and fluctuation is comparatively large, wear resistance is bad, reach certain temperature after antioxidant property low, easily to be lighted and flame has the problems such as the spontaneous tendency spread, these problems make it apply widely to be restricted.Because these problems great majority of titanium alloy not caused by material monolithic performance, and main relevant to surface property, so solving these problems with process for modifying surface is more satisfactory selections.
Process for modifying surface, while raising surface property, maintains whole titanium alloy mechanical property and proportion is low, specific tenacity advantages of higher.Differential arc oxidation, plasma spraying, supersonic spray coating, ion implantation, the technology such as electron beam deposition, nitride laser, double-layer glow ion penetration all can be applied to titanium alloy surface modification; Although but these technology improving the frictional wear of titanium alloy, high temperature oxidation, the aspect of performance such as fire-retardant achieve certain effect, but these sufacings also have respective limitation, ubiquity or coat thin, or shock resistance is poor, or with matrix in conjunction with weak, or significantly reduce the shortcomings such as matrix fatigue property, current demand can not be met, therefore need development to have more high performance coated material and technology of preparing.
Summary of the invention
For prior art above shortcomings, technical problem to be solved by this invention is: how to provide a kind of multi-principal elements alloy and for the method to titanium alloy surface process, make this top coat and titanium alloy substrate metallurgical binding, wear resistance and the high temperature oxidation resistance of titanium alloy can be improved simultaneously, and titanium fire can be prevented.
To achieve these goals, the present invention adopts following technical scheme: a kind of multi-principal elements alloy, in molfraction, comprises following component: 18-30 part Zr, 18-30 part Ni, 18-30 part Si, 18-30 part Ta, 1 ~ 10 part of Ti and 2-5 part CeO
2.
Above-mentioned multi-principal elements alloy is used for the method to titanium alloy surface process, comprises the steps:
1) titanium alloy base material acetone or dehydrated alcohol are cleaned, and carry out sandblasting roughening treatment;
2) according to above-mentioned formulated multi-principal elements alloy powder, the titanium alloy substrate surface of multi-principal elements alloy powder spraying after step 1) process will prepared with plasma spraying equipment; Wherein, the granularity of described multi-principal elements alloy powder is-100 ~+500 orders; Carry out argon shield in spraying process, coating thickness is 0.3 ~ 0.6mm;
3) CO of peak power>=1000W is used
2laser apparatus is to step 2) process after plasma spraying surface carry out re melting process, adopt argon gas to carry out cooling and protecting in reflow process, obtain described multi-principal elements alloy coating at titanium alloy surface; Wherein, control flow is 1.5-2.5L/min, and regulate laser power scope to be 600-900W, scanning speed is 3-5mm/s, and spot diameter is 3-4.5mm.
Compared to existing technology, the present invention has following beneficial effect:
1, the multi-principal elements alloy coating that prepared by the present invention make use of the feature such as high entropy effect, the slowly diffusional effect of multi-principal elements alloy, nanophase strengthening, superelevation lattice distortion and " cocktail effect ", by the collaborative compatibility effect between each element, significantly improve wear resistance and the high temperature oxidation resistance of titanium alloy, effectively prevent titanium fire; Verify by experiment, the titanium alloy relative wear resistance being covered with this coating is 6.9 ~ 7.5 times of titanium alloy substrate, and oxidation weight gain is 0.29 ~ 0.32 times of titanium alloy substrate, and in fire retardancy test, also combustion phenomena does not occur, and creates beyond thought technique effect.
2, the present invention adopts spraying-laser remolten method to prepare multi-principal elements alloy coating at titanium alloy surface, in conjunction with re melting process, utilize thermal source ingredient melting by what the most easily melt in alloy, the liquid phase produced contributes to the strengthening of diffusion process and the infiltration of composition, the result of fusing makes the land of hot spray coating and matrix become densification from originally stacking lamellar structure and organize more uniformly, hole minimizing even disappears, improve the bonding strength between coating and matrix and coating inner quality, promote the uniform fusion of different element, give play to the collaborative effect of design mix.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail.The implementation case is implemented under premised on the technology of the present invention, now provide detailed embodiment and concrete operating process, illustrate that the present invention is creative, but protection scope of the present invention is not limited to following embodiment.The pharmaceutical chemicals used in following embodiment if no special instructions, is common commercially available prod.
embodiment 1
One, a multi-principal elements alloy, in molfraction, comprises following composition: 23 parts of Zr, 28 parts of Ni, 28 parts of Si, 18 parts of Ta, 1 part of Ti, 2 parts of CeO
2.
Two, above-mentioned multi-principal elements alloy is used for the method to titanium alloy surface process, comprises the steps:
1) TC4 titanium alloy base material acetone is cleaned; After having cleaned, carry out sandblasting roughening treatment.
2) with plasma spraying equipment by the titanium alloy substrate surface of multi-principal elements alloy powder spraying good for proportioning after step 1) process; Wherein, the granularity of described multi-principal elements alloy powder is-200 ~+350 orders; Argon shield is carried out, coating thickness 0.3mm in spraying process.
3) employing peak power is the TJ-HL-T5000 type CO of 5kW
2laser apparatus is to step 2) process after plasma spraying surface carry out re melting process, adopt argon gas to carry out cooling and protecting in reflow process, through laser remolten processing after can obtain densification, the more much higher pivot alloy coat of bonding strength; Wherein, control flow is 2.0L/min, and adjustment laser power is 680W, and scanning speed is 5mm/s, and spot diameter is 4.5mm, and overlapping rate is 30%.
The titanium alloy with multi-principal elements alloy coating that the present embodiment is obtained and TC4 titanium alloy substrate, in atmosphere with GCr15 to rubbing 1 hour, the titanium alloy relative wear resistance of result display coating is 6.9 times of TC4 titanium alloy substrate.In 800 DEG C of air, carry out oxidation 50 hours to coating with without the titanium alloy of coating, the titanium alloy oxidation weight gain of result display coating is 0.32 times of titanium alloy substrate.Fire retardancy test adopts sessile drop method to carry out, to melt and the TC4 titanium alloy drop burnt drips to TC4 titanium alloy specimen surface, sample is very fast to burn together with drop, and will melt and the titanium alloy drop burnt drip to coating sample surface time, until drop burns cinder, the titanium alloy sample of the coating of all participation tests does not all burn; Experiment shows that this coating improves the abrasion resistant fire blocking high temperature oxidation resistance of titanium alloy.
embodiment 2
one,a kind of multi-principal elements alloy, in molfraction, comprises following composition: 28 parts of Zr, 22 parts of Ni, 22 parts of Si, 23 parts of Ta, 3 parts of Ti, 2 parts of CeO
2.
Two, above-mentioned multi-principal elements alloy is used for the method to titanium alloy surface process, comprises the steps:
1) TA15 titanium alloy base material dehydrated alcohol is cleaned; After having cleaned, carry out sandblasting roughening treatment.
2) with plasma spraying equipment by the titanium alloy substrate surface of multi-principal elements alloy powder spraying good for proportioning after step 1) process; Wherein, the granularity of described multi-principal elements alloy powder is-200 ~+350 orders; Argon shield is carried out, coating thickness 0.5mm in spraying process.
3) employing peak power is the TJ-HL-T5000 type CO of 5kW
2laser apparatus is to step 2) process after plasma spraying surface carry out re melting process, adopt argon gas to carry out cooling and protecting in reflow process, through laser remolten processing after can obtain densification, the more much higher pivot alloy coat of bonding strength; Wherein, control flow is 2.0L/min, and adjustment laser power is 850W, and scanning speed is 3mm/s, and spot diameter is 3.5mm, and overlapping rate is 30%.
The titanium alloy with multi-principal elements alloy coating that the present embodiment is obtained and TA15 titanium alloy substrate, in atmosphere with GCr15 to rubbing 1 hour, the titanium alloy relative wear resistance of result display coating is 7.5 times of TA15 titanium alloy substrate.In 800 DEG C of air, carry out oxidation 50 hours to coating with without the titanium alloy of coating, the titanium alloy oxidation weight gain of result display coating is 0.29 times of titanium alloy substrate.Fire retardancy test adopts sessile drop method to carry out, to melt and the TA15 titanium alloy drop burnt drips to TA15 titanium alloy specimen surface, sample is very fast to burn together with drop, and will melt and the titanium alloy drop burnt drip to coating sample surface time, until drop burns cinder, the titanium alloy sample of the coating of all participation tests does not all burn; Experiment shows that this coating improves the abrasion resistant fire blocking high temperature oxidation resistance of titanium alloy.
What finally illustrate is, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (9)
1. a multi-principal elements alloy, is characterized in that, in molfraction, comprises following component: 18-30 part Zr, 18-30 part Ni, 18-30 part Si, 18-30 part Ta, 1 ~ 10 part of Ti and 2-5 part CeO
2.
2. multi-principal elements alloy according to claim 1, is characterized in that, in molfraction, comprise following composition: 28 parts of Zr, 22 parts of Ni, 22 parts of Si, 23 parts of Ta, 3 parts of Ti and 2 part CeO
2.
3. multi-principal elements alloy described in claim 1 or 2 is used for the method to titanium alloy surface process, it is characterized in that, comprises the steps:
1) titanium alloy base material acetone or dehydrated alcohol are cleaned, and carry out sandblasting roughening treatment;
2) according to the arbitrary described formulated multi-principal elements alloy powder of claim 1 or 2, the titanium alloy substrate surface of multi-principal elements alloy powder spraying after step 1) process will prepared with plasma spraying equipment; Wherein, the granularity of described multi-principal elements alloy powder is-100 ~+500 orders; Carry out argon shield in spraying process, coating thickness is 0.3 ~ 0.6mm;
3) CO of peak power>=1000W is used
2laser apparatus is to step 2) process after plasma spraying surface carry out re melting process, adopt argon gas to carry out cooling and protecting in reflow process, obtain described multi-principal elements alloy coating at titanium alloy surface; Wherein, control flow is 1.5-2.5L/min, and regulate laser power scope to be 600-900W, scanning speed is 3-5mm/s, and spot diameter is 3-4.5mm.
4. multi-principal elements alloy is used for method to titanium alloy surface process according to claim 3, it is characterized in that, step 2) described in the granularity of multi-principal elements alloy powder be-200 ~+350 orders.
5. multi-principal elements alloy is used for method to titanium alloy surface process according to claim 3, it is characterized in that, step 2) described in coating thickness be 0.5mm.
6. multi-principal elements alloy is used for the method to titanium alloy surface process according to claim 3, it is characterized in that, regulates laser power to be 850W in step 3).
7. multi-principal elements alloy is used for the method to titanium alloy surface process according to claim 3, and it is characterized in that, in step 3), scanning speed is 3mm/s.
8. multi-principal elements alloy is used for the method to titanium alloy surface process according to claim 3, and it is characterized in that, in step 3), spot diameter is 3.5mm.
9. multi-principal elements alloy is used for the method to titanium alloy surface process according to claim 3, and it is characterized in that, controlling overlapping rate in step 3) is 30%.
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| CN201510857736.5A CN105331869B (en) | 2015-11-30 | 2015-11-30 | A kind of multi-principal elements alloy and its method for processing titanium alloy surface |
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| CN201510857736.5A CN105331869B (en) | 2015-11-30 | 2015-11-30 | A kind of multi-principal elements alloy and its method for processing titanium alloy surface |
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| CN105331869A true CN105331869A (en) | 2016-02-17 |
| CN105331869B CN105331869B (en) | 2017-07-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107537065A (en) * | 2017-07-11 | 2018-01-05 | 吉林大学 | High-entropy alloy joint prosthesis based on in-situ test couples bionical construction method |
| CN109811289A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Surface modified titanium alloy and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537065A (en) * | 2017-07-11 | 2018-01-05 | 吉林大学 | High-entropy alloy joint prosthesis based on in-situ test couples bionical construction method |
| CN109811289A (en) * | 2019-02-27 | 2019-05-28 | 中国科学院宁波工业技术研究院慈溪生物医学工程研究所 | Surface modified titanium alloy and its preparation method and application |
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| CN105331869B (en) | 2017-07-07 |
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