CN106756236A - A kind of TC19 titanium alloy composite materials and its preparation method and application - Google Patents
A kind of TC19 titanium alloy composite materials and its preparation method and application Download PDFInfo
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- CN106756236A CN106756236A CN201611268172.2A CN201611268172A CN106756236A CN 106756236 A CN106756236 A CN 106756236A CN 201611268172 A CN201611268172 A CN 201611268172A CN 106756236 A CN106756236 A CN 106756236A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- 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
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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
- C23C24/106—Coating with metal alloys or metal elements only
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C2204/00—End product comprising different layers, coatings or parts of cermet
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Abstract
The invention discloses a kind of TC19 titanium alloy composite materials, the material is made up of TC19 titanium alloy substrates with high-entropy alloy layer；The invention also discloses the preparation method of this composite：By the constitution element of high-entropy alloy dispensing in proportion, the surface of TC19 titanium alloys is then deposited in the presence of laser.This composite not only possesses the advantage of titanium alloy high specific strength, additionally it is possible to use in high temperature environments, compensate for the shortcoming of conventional titanium alloy.
Description
Technical field
The present invention relates to titanium alloy field, and in particular to a kind of anti-oxidant titanium alloy composite material and preparation method thereof and should
With.
Background technology
Titanium alloy is a kind of metal material of excellent performance, and its density is low, intensity is high, and its specific strength is in all metals
Highest.Thus, titanium alloy is widely applied in fields such as national defence, Aero-Space.But, the resistance to elevated temperatures of titanium alloy
Bad, at high temperature, titanium alloy is very easy to oxidation, thus limits its application.
The patent of invention of Publication No. 105603483A discloses a kind of preparation side of titanium-base alloy high temperature coatings
Method, comprises the following steps：1) oxide on surface of titanium-based alloy matrix is removed first, is then cleaned, is dried；2) in proportion by nothing
The mixing of water-ethanol, water and precursor alkyl silicate, pH of mixed to 2.0~6.0 is adjusted with acid, and 2~48h is stirred at room temperature, is obtained
To precursor solution；3) precursor solution for preparing is added in two slot electrodes, using titanium-based alloy matrix as working electrode, platinum
, used as to electrode, in 1-10cm, control electric current density is -0.1mAcm for electrode spacing control for piece or graphite-2~-5.0mA
cm-2, sedimentation time is 30s~2000s, and washing obtains micro-nano oxide coating after 40~150 DEG C of drying；4) will covering
There is the titanium-base alloy of micro-nano oxide coating in atmosphere in 10~60min is heat-treated at 600~700 DEG C, that is, titanium-based is obtained
Alloy high temperature coatings.The present invention is simple, has excellent adhesion between the coating and matrix of acquisition, can
Significantly improve titanium-aluminium alloy high-temperature oxidation resistance.
It is wear-resistant compound that the patent of invention of Publication No. 104947107A provides a kind of titanium or titanium alloy surface oxidation-resistant
Coating and preparation method thereof, belongs to technical field of surface.The composite coating is anti-oxidant by internal layer oxygen barrier layer and outer abrasion resistant
Layer composition；Oxygen barrier layer is the aluminized coating of rich aluminium, and its main component is TiAl3, wear-resisting anti oxidation layer is Al for composition2O3And TiO2
High-hardness ceramic.The method includes 1, titanium or titanium alloy surface pretreatment；2nd, titanium or Pack Aluminizing on Ti Alloys are processed；3rd, titanium or
Titanium-alloy surface micro-arc oxidation treatment.The method is simple, is adapted to useful industrially；The composite coating high temperature oxidation resistance will get well
In existing protective coating, solve the problems, such as that common aluminising forms penetrating crack and sprayed coating adhesion is low, solve titanium conjunction
The problems such as golden common differential arc oxidation hardness is not enough, nitridation modified layer is relatively thin, meets most of titanium alloy parts to wearability
It is required that.
The patent of invention of Publication No. 103103593A discloses the surface ceramic oxidation of a kind of aluminium, magnesium, titanium or its alloy
Method, be related to the surface ceramic oxidation technology field of a kind of metal and its alloy, by with aluminium, magnesium, titanium or its alloy as material
Workpiece is put in the electrolytic solution, and with the workpiece as anode, additional cathode around it is subject to 500V electricity between the anode and cathode
Pressure, while be scanned in workpiece surface with laser beam, so as to aoxidize out in-situ authigenic into ceramic membrane in workpiece surface.Using this
Inventive method can aoxidize out ceramic membrane in aluminium, magnesium, titanium or its alloy surface in-situ authigenic, so as to aluminium, magnesium, titanium or its alloy
For the workpiece of material is strengthened, its wearability and corrosion resistance are improved.
The patent of invention of Publication No. 105543798A provides a kind of side for improving titanium-base alloy high temperature oxidation resistance
Method, comprises the following steps：1) oxide on surface of titanium-based alloy matrix is removed, is then cleaned, is dried；2) ion implantation is used
To injecting characteristic ion in titanium-based alloy matrix；Characteristic ion is the one kind or any several in Cr, Y, Nb, F, Cl ion；3)
Absolute ethyl alcohol, water and precursor alkyl silicate are mixed in proportion, then adjusts mixed system pH to 2.0~6.0, stirred at room temperature
Mix and obtain precursor solution；4) precursor solution for preparing is added in two slot electrodes, is closed with the titanium-based for being filled with characteristic ion
Gold is negative electrode, and platinized platinum or graphite carry out electro-deposition as to electrode, is dried after working electrode is washed after the completion of deposition, is obtained
Micro-nano oxide coating；5) titanium-base alloy that will be covered with micro-nano oxide coating is heat-treated in atmosphere, obtains anti-height
Warm oxide covering, significantly improves the high temperature oxidation resistance of titanium-base alloy.
The patent of invention of Publication No. 105331973A disclose a kind of titanium alloy surface prepare Nb titanium aluminium base alloys high resist
The method of oxide covering.The method is to utilize CO2Fabricated in situ between the lower Ti-Al-Nb complex element powder of laser beam effect
Reaction and heat treatment, Nb titanium aluminium base alloys coating high is prepared in titanium alloy surface.Coating preparation process includes：Titanium alloy surface is pre-
Treatment, powder is prepared and ball milling, powder be preset, the heat treatment of selective laser sintering, coating, antioxygenic property test and microscopic structure
Seven parts of analysis.The performance test results show that the invention can effectively reduce vigorous oxidation of the titanium alloy in hot environment,
Increase substantially the titanium alloy temperature in use limit；The invention provides a kind of cycle is short, integrated cost be low, flexibility degree is high
Coating production；The method can be on the premise of little amplitude influences alloy coat high-temperature oxidation resistance, to coating composition
Proportioning is adjusted flexibly, and is obtained the Nb titanium aluminium base alloys two-phase high that consistency is high, thickness is uniform, antioxygenic property is excellent and is applied
Layer.
Above method can improve the applied at elevated temperature performance of titanium alloy, but typically all reduce the mechanical property of material surface
Energy.
The content of the invention
Goal of the invention：In order to improve the temperature in use of titanium alloy, the technical problems to be solved by the invention there is provided one
Plant TC19 titanium alloy composite materials.
The technical problem also to be solved of the invention there is provided a kind of preparation method of TC19 titanium alloy composite materials.
The technical problem also to be solved of the invention there is provided a kind of application of TC19 titanium alloy composite materials.
The temperature in use of conventional titanium alloy is no more than 650 degrees Celsius, and the present invention is using the method for laser cladding, system
Standby titanium alloy-high-entropy alloy composite, can bring up to more than 800 degrees Celsius by the temperature in use of titanium alloy.
To achieve the above object, the technical solution adopted by the present invention is：A kind of TC19 titanium alloy composite materials, the alloy by
TC19 titanium alloy substrates are constituted with high-entropy alloy layer.
Preferably, high-entropy alloy presses atomic percent includes following component：Ti：V is 1：1.5 ~ 2, V：Cr is 1：0.9~
1.1, V：Al is 1：0.9 ~ 1.1, V：Fe is 1：0.9 ~ 1.1, V：Si is 1：0.9 ~ 1.1, V：Zr is 1：0.4~0.5.
Preferably, the thickness of above-mentioned high-entropy alloy layer is 100-5000 microns.
The preparation method of above-mentioned TC19 titanium alloy composite materials, comprises the following steps：
1）Prepare dusty raw materials according to above-mentioned high-entropy alloy element ratio, and be well mixed；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using laser in TC19 titanium alloy surface deposition high-entropy alloys, design parameter is：Laser is swept
Speed 4mm/s is retouched, spot diameter is 2.8mm, and sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer and base
Body is well combined；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
Application of the above-mentioned TC19 titanium alloy composite materials at aspects such as Aero-Space, the vehicles.
Beneficial effect：The present invention has advantages below：A kind of TC19 titanium alloys can be prepared using the method for the present invention to answer
Condensation material, can bring up to more than 800 degrees Celsius, far above the temperature in use of conventional titanium alloy by the temperature in use of titanium alloy
（Generally below 650 degrees Celsius）.This is, because high-entropy alloy layer has excellent high-temperature behavior, can to protect the titanium alloy of inside
It is not oxidized.Also, because high-entropy alloy has high hardness, therefore, the present invention is closed than the titanium protected using coating surface
The case hardness of gold is higher.High-entropy alloy of the invention is not using rare earth element costly, and low cost, effect is good.
Specific embodiment
The present invention is further illustrated with reference to specific embodiment.
Embodiment 1：The preparation of TC19 titanium alloy composite materials
1）According to Ti：V：Cr：Al：Fe：Si：Zr =1：2：1.9：1.8：2.1：1.9：1 atomic ratio is preparing metal powder, mixing
Uniformly；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using carbon dioxide laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser
Device sweep speed 4mm/s, spot diameter is 2.8mm, and sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer
It is well combined with matrix；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
Embodiment 2：The preparation of TC19 titanium alloy composite materials
1）According to Ti：V：Cr：Al：Fe：Si：Zr=1：1.5：1.5：1.5：1.6：1.4：0.75 atomic ratio is preparing metal powder,
It is well mixed；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using carbon dioxide laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser
Device sweep speed 4mm/s, spot diameter is 2.5mm, and sweep span 1.5mm, powder feed rate is 2g/min, until final cladding layer
It is well combined with matrix；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
Embodiment 3：The preparation of TC19 titanium alloy composite materials
1）According to Ti：V：Cr：Al：Fe：Si：Zr =1：2：2.2：1.8：2.2：2：0.9 atomic ratio is preparing metal powder, mixing
Uniformly；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using carbon dioxide laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser
Device sweep speed 4mm/s, spot diameter is 2.8mm, and sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer
It is well combined with matrix；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
Embodiment 4：The preparation of TC19 titanium alloy composite materials
1）According to Ti：V：Cr：Al：Fe：Si：Zr =1：2：1.8： 2.2：1.8：1.8：0.8 atomic ratio is preparing metal powder,
It is well mixed；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using carbon dioxide laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser
Device sweep speed 4mm/s, spot diameter is 2.8mm, and sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer
It is well combined with matrix；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
Embodiment 5：The preparation of TC19 titanium alloy composite materials
1）According to Ti：V：Cr：Al：Fe：Si：Zr =1：2：1.9：2.1：1.9：2.2：0.8 atomic ratio is preparing metal powder, is mixed
Close uniform；
2）Prepare TC19 titanium alloy substrates, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using carbon dioxide laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser
Device sweep speed 4mm/s, spot diameter is 2.8mm, and sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer
It is well combined with matrix；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
High temperature oxidation resistance comparative study：Oxidizing atmosphere guarantor by embodiment 1-5 and TC19 titanium alloys at 800 degrees Celsius
Temperature 24 hours, finds that the surface of TC19 titanium alloys produces 58 microns of oxide layers after taking-up, and there is crackle on surface, it is impossible to which matrix is produced
Raw preferably protection, therefore carrying out over time, TC19 alloys also may proceed to oxidation；And the surface of embodiment 1-5 is all formed
Fine and close oxide-film, the thickness of oxide-film is followed successively by 9,6,8,3,8 microns, because diaphragm is very fine and close, therefore can be right
Matrix is protected well.TC19 is than the milli gram/cm of weightening 11.2 before experiment, and the weightening of embodiment 1-5 after experiment
Respectively 2.3,2.4,1.9,2.2,2.7 millis gram/cm, it is known that material of the invention has more preferable high temperature resistant, antioxygen
Change performance.
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (8)
1. a kind of TC19 titanium alloy composite materials, it is characterised in that the material is by TC19 titanium alloy substrates and high-entropy alloy layer structure
Into.
2. a kind of TC19 titanium alloy composite materials according to claim 1, it is characterised in that described high-entropy alloy by
Titanium, vanadium, chromium, aluminium, iron, silicon, zr element are constituted.
3. a kind of TC19 titanium alloy composite materials according to claim 1, it is characterised in that the thickness of described high-entropy alloy
Spend is 100-5000 microns.
4. a kind of TC19 titanium alloy composite materials according to claim 1, it is characterised in that described high-entropy alloy layer
Composition proportion is constituted according to atomic percent：Ti：V is 1：1.5 ~ 2, V：Cr is 1：0.9 ~ 1.1, V：Al is 1：0.9 ~ 1.1, V：
Fe is 1：0.9 ~ 1.1, V：Si is 1：0.9 ~ 1.1, V：Zr is 1：0.4~0.5.
5. a kind of TC19 titanium alloy composite materials according to claim 4, it is characterised in that described high-entropy alloy is used
It is prepared by the method for laser cladding.
6. the preparation method of the TC19 titanium alloy composite materials described in any one of claim 1 ~ 5, it is characterised in that including following
Step：
1）Prepare dusty raw materials according to above-mentioned high-entropy alloy element ratio, and be well mixed；
2）Prepare TC19 titanium alloy substrates, clean up surface；
3）Using laser in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser scanning speed 4mm/s, hot spot
A diameter of 2.8mm, sweep span 1.6mm, powder feed rate is 2g/min, until final cladding layer and matrix are well combined；
4）Air cooling, thus obtains TC19 titanium alloys-high-entropy alloy composite.
7. the preparation method of TC19 titanium alloy composite materials according to claim 6, it is characterised in that the laser is
CO2 lasers.
8. the TC19 titanium alloy composite materials described in any one of claim 1 ~ 5 the aspects such as Aero-Space, the vehicles should
With.
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Cited By (3)
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| CN108531776A (en) * | 2018-05-28 | 2018-09-14 | 中南大学 | A kind of high-strength titanium matrix composite of brake system of car powder metallurgy and preparation method thereof |
| CN112553667A (en) * | 2020-11-23 | 2021-03-26 | 西安工业大学 | AlFexCrCoNi high-entropy alloy surface ceramic-forming method |
| CN114855241A (en) * | 2022-04-21 | 2022-08-05 | 中南大学 | Preparation method of in-situ self-generated wear-resistant ceramic coating on surface of refractory medium-high entropy alloy |
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| CN114855241A (en) * | 2022-04-21 | 2022-08-05 | 中南大学 | Preparation method of in-situ self-generated wear-resistant ceramic coating on surface of refractory medium-high entropy alloy |
| CN114855241B (en) * | 2022-04-21 | 2023-12-05 | 中南大学 | Preparation method of refractory medium-high entropy alloy surface in-situ self-generated wear-resistant ceramic coating |
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