CN106637202A - High-temperature-resistant titanium alloy composite material, and preparation method and application thereof - Google Patents
High-temperature-resistant titanium alloy composite material, and preparation method and application thereof Download PDFInfo
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- CN106637202A CN106637202A CN201611268111.6A CN201611268111A CN106637202A CN 106637202 A CN106637202 A CN 106637202A CN 201611268111 A CN201611268111 A CN 201611268111A CN 106637202 A CN106637202 A CN 106637202A
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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
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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Abstract
The invention discloses a high-temperature-resistant titanium alloy composite material. The material is composed of a titanium alloy substrate and a high-entropy alloy layer. The invention also discloses a preparation method of the composite material. The preparation method comprises the following steps: proportionally preparing component elements of the high-entropy alloy, and depositing on the surface of the titanium alloy under the action of laser. The composite material not only has the advantage of high specific strength of the titanium alloy, but also can be used under a high-temperature environment, thereby compensating for the defect of the traditional titanium alloy.
Description
Technical field
The present invention relates to high temperature resistant titanium alloy field of compound material, and in particular to a kind of high temperature resistant titanium alloy composite and
Its preparation method and application.
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. 101550496B provides a kind of high-temperature anti-oxidation TiCp/Ti alloy-base composite materials
Preparation method, it is related to a kind of preparation method of high-temperature oxidation resistant Ti alloy-base composite materials.It solves current titanium alloy
High-temperature oxidation resistance it is poor, easily there is oxidation in hot environment, oxide layer occur and come off, cause the size of titanium alloy continuous
Diminution, the significantly reduced problem of its mechanical performance, and the equally distributed particulate metal matrix composites high temperature of TiCp and TiBw are anti-
Oxidation susceptibility improves DeGrain, however it remains low using temperature, high-temperature service time short defect.Preparation method：By C powder
With the mixed powder of Ti alloyed powders ball milling, then vacuum-sintering.The TiCp/Ti alloy-base composite materials that the inventive method is prepared are being improved
On the basis of Ti alloy mechanical properties, the high-temperature oxidation resistance of composite is greatly improved, aoxidized in 700 DEG C of environment
150h, only top layer titanium alloy is aoxidized, and is come off generation without oxide layer, therefore has the advantages that the high-temperature service time is long.
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 process.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
Require.
The patent of invention of Publication No. 105331973A disclose a kind of titanium alloy surface prepare high Nb titanium aluminium base alloys 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, in titanium alloy surface high Nb titanium aluminium base alloys coating is prepared.Coating preparation process includes：Titanium alloy surface is pre-
Process, 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 titanium alloy and use temperature extremes；The invention provides that 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 high Nb titanium aluminium base alloys two-phase that consistency is high, thickness is uniform, antioxygenic property is excellent and is applied
Layer.
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 is adjusted to 2.0～6.0 with acid, and 2～48h is stirred under 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, is washed after 40～150 DEG C of drying, obtains micro-nano oxide coating；4) will cover
The titanium-base alloy for having micro-nano oxide coating is heat-treated in atmosphere 10～60min 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.
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 use temperature of titanium alloy, the technical problem to be solved there is provided one
Plant high temperature resistant titanium alloy composite.
The technical problem also to be solved of the invention there is provided a kind of preparation method of high temperature resistant titanium alloy composite.
The technical problem also to be solved of the invention there is provided a kind of application of high temperature resistant titanium alloy composite.
The use temperature 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 use temperature of titanium alloy.
For achieving the above object, the technical solution used in the present invention is：A kind of high temperature resistant titanium alloy composite, the alloy
It is made up of with high-entropy alloy layer titanium alloy substrate,.
Preferably, high-entropy alloy presses atomic percent including 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：Si is 1：0.9~1.1.
Preferably, the thickness of above-mentioned high-entropy alloy layer is 100-5000 microns.
The preparation method of above-mentioned high temperature resistant titanium alloy composite, comprises the following steps：
1）Prepare dusty raw materials according to above-mentioned high-entropy alloy element ratio, and be well mixed；
2）Prepare titanium alloy substrate, remove removing oxide layer, clean up surface；
3）In an inert atmosphere using laser instrument in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser scans speed
Degree 3mm/s, spot diameter is 2.5mm, and sweep span 1.5mm, powder feed rate is 2g/min, until final cladding layer and matrix are tied
Close good；
4）Air cooling, thus obtains titanium alloy-high-entropy alloy composite.
Application of the above-mentioned high temperature resistant titanium alloy composite at aspects such as Aero-Space, the vehicles.
Beneficial effect：The present invention has advantages below：A kind of high temperature resistant titanium alloy can be prepared using the method for the present invention
Composite, can bring up to more than 800 degrees Celsius, far above the use temperature of conventional titanium alloy by the use temperature of titanium alloy
（Generally below 650 degrees Celsius）.This is the titanium alloy that inside can be protected because high-entropy alloy layer has excellent high-temperature behavior
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.The high-entropy alloy of the present 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 high temperature resistant titanium alloy composite
1）According to Ti：V：Cr：Al：Si=1：2：1.9：1.8：2.1 atomic ratio is preparing metal powder, is well mixed；
2）Prepare TC4 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 3mm/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 titanium alloy-high-entropy alloy composite.
Embodiment 2：The preparation of high temperature resistant titanium alloy composite
1）According to Ti：V：Cr：Al：Si=1：1.5：1.5：1.5：1.6 atomic ratio is preparing metal powder, is well mixed；
2）Prepare TA5 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 3mm/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 titanium alloy-high-entropy alloy composite.
Embodiment 3：The preparation of high temperature resistant titanium alloy composite
1）According to Ti：V：Cr：Al：Si=1：2：1.8： 2.2：1.8 atomic ratio is preparing metal powder, is well mixed；
2）Prepare TA2 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 3mm/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 titanium alloy-high-entropy alloy composite.
Embodiment 4：The preparation of high temperature resistant titanium alloy composite
1）According to Ti：V：Cr：Al：Si=1：2：2.2：1.8：2.2 atomic ratio is preparing metal powder, is well mixed；
2）Prepare TC4 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 3mm/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 titanium alloy-high-entropy alloy composite.
Embodiment 5：The preparation of high temperature resistant titanium alloy composite
1）According to Ti：V：Cr：Al：Si=1：2：1.9：2.1：1.9 atomic ratio is preparing metal powder, is well mixed；
2）Prepare TC1 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 3mm/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 titanium alloy-high-entropy alloy composite.
High temperature oxidation resistance comparative study：By the oxidizing atmosphere guarantor of embodiment 1-5 and TC4 titanium alloys at 800 degrees Celsius
Temperature 24 hours, the surface that TC4 titanium alloys are found after taking-up produces 50 microns of oxide layers, and there is crackle on surface, it is impossible to which matrix is produced
Raw preferably protection, therefore carrying out over time, TC4 alloys also may proceed to oxidation；And the surface of embodiment 1-5 all defines
Fine and close oxide-film, the thickness 5-8 microns of oxide-film, because diaphragm is very fine and close, therefore can be carried out well to collective
Protection.TC4 is than the milli gram/cm of weightening 10.3 before experiment after experiment, and the weightening of embodiment 1-5 be respectively 2.8,3.1,
3.2nd, 2.9,2.7 milli gram/cm, it is known that the material of the present invention has more preferable high temperature resistant, antioxygenic property.
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 high temperature resistant titanium alloy composite, it is characterised in that the material is made up of titanium alloy substrate with high-entropy alloy layer.
2. a kind of high temperature resistant titanium alloy composite according to claim 1, it is characterised in that described high-entropy alloy by
Titanium, vanadium, chromium, aluminium, element silicon are constituted.
3. a kind of high temperature resistant titanium alloy composite according to claim 1, it is characterised in that described high-entropy alloy
Thickness is 100-5000 microns.
4. a kind of high temperature resistant titanium alloy composite according to claim 1, it is characterised in that described high-entropy alloy layer
Composition proportion consist of 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：Si is 1：0.9~1.1.
5. a kind of high temperature resistant titanium alloy composite according to claim 4, it is characterised in that described high-entropy alloy is adopted
Prepared with the method for laser cladding.
6. the preparation method of the high temperature resistant titanium alloy composite described in any one of claim 1 ~ 5, it is characterised in that include with
Lower step：
1）Prepare dusty raw materials according to above-mentioned high-entropy alloy element ratio, and be well mixed；
2）Prepare titanium alloy substrate, clean up surface；
3）Using laser instrument in titanium alloy surface deposition high-entropy alloy, design parameter is：Laser scanning speed 3mm/s, hot spot
A diameter of 2.5mm, sweep span 1.5mm, powder feed rate is 2g/min, until final cladding layer and matrix are well combined；
4）Air cooling, thus obtains titanium alloy-high-entropy alloy composite.
7. the preparation method of high temperature resistant titanium alloy composite according to claim 6, it is characterised in that the laser instrument
For CO2 laser instruments.
8. the high temperature resistant titanium alloy composite described in any one of claim 1 ~ 5 is at aspects such as Aero-Space, the vehicles
Using.
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| CN201611268111.6A CN106637202A (en) | 2016-12-31 | 2016-12-31 | High-temperature-resistant titanium alloy composite material, and preparation method and application thereof |
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| CN201611268111.6A CN106637202A (en) | 2016-12-31 | 2016-12-31 | High-temperature-resistant titanium alloy composite material, and preparation method and application thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763125A (en) * | 2019-01-18 | 2019-05-17 | 青岛滨海学院 | A kind of high entropy alloy coating and its preparation process, application of high temperature wear resistant |
| CN115821208A (en) * | 2022-12-06 | 2023-03-21 | 西北有色金属研究院 | Accident-resistant high-entropy alloy coating for nuclear fuel cladding pipe and preparation method thereof |
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| CN1353204A (en) * | 2000-11-09 | 2002-06-12 | 叶均蔚 | High-irregularity multi-element alloy |
| US20160326616A1 (en) * | 2015-05-04 | 2016-11-10 | Seoul National University R&Db Foundation | Entropy-controlled bcc alloy having strong resistance to high-temperature neutron radiation damage |
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2016
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1353204A (en) * | 2000-11-09 | 2002-06-12 | 叶均蔚 | High-irregularity multi-element alloy |
| US20160326616A1 (en) * | 2015-05-04 | 2016-11-10 | Seoul National University R&Db Foundation | Entropy-controlled bcc alloy having strong resistance to high-temperature neutron radiation damage |
Non-Patent Citations (2)
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| C. HUANG, ET AL.: "Dry sliding wear behavior of laser clad TiVCrAlSi high entropy alloy coatings on Ti-6Al-4V substrate", 《MATERIALS AND DESIGN》 * |
| C. HUANG, ET AL.: "Thermal stability and oxidation resistance of laser clad TiVCrAlSi high entropy alloy coatings on Ti-6Al-4V alloy", 《SURFACE & COATINGS TECHNOLOGY》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109763125A (en) * | 2019-01-18 | 2019-05-17 | 青岛滨海学院 | A kind of high entropy alloy coating and its preparation process, application of high temperature wear resistant |
| CN115821208A (en) * | 2022-12-06 | 2023-03-21 | 西北有色金属研究院 | Accident-resistant high-entropy alloy coating for nuclear fuel cladding pipe and preparation method thereof |
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Application publication date: 20170510 |