CN102268568B - TiAl-based alloy with excellent high temperature oxidation resistance and creep resistance suitable for casting - Google Patents
TiAl-based alloy with excellent high temperature oxidation resistance and creep resistance suitable for casting Download PDFInfo
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Abstract
The invention discloses a TiAl-based alloy with excellent high temperature oxidation resistance and creep resistance suitable for casting and the alloy belongs to the gamma-TiAl alloy. The TiAl-based alloy comprises the following components by atomic percent: 44.0-48.0% of Al, 1.0-3.0% of Nb, 0.1-3.0% of Mo, 0-0.8% of Si or/and 0-0.6% of C, and the balance of Ti and impurity elements, wherein the sum of the atomic percents of Si and C is 0.1-0.9%. The TiAl-based alloy disclosed by the invention has good high temperature performances and casting fluidity and is suitable for the casting of thin-walled parts; methods such as chemical treatment, thermal spraying and ion implantation which are used to increase the oxidation resistance, are not required to treat the surface of the alloy at 850-950 DEG C; and the TiAl-based alloy is particularly suitable to cast the gasoline engine supercharger turbine rotor which can work below 900-950 DEG C.
Description
Technical field
The present invention relates to a kind of superalloy art, particularly the excellent titanium aluminium base alloy that is fit to casting of a kind of high-temperature oxidation resistant creep property.
Background technology
Along with the motor performance such as Aeronautics and Astronautics, automobile, naval vessel improve constantly, the performance of high-temperature material is had higher requirement, i.e. higher intensity, antioxidant property and lighter density etc.γ-TiAl base alloy material has the advantages such as good hot strength, creep resistance and antioxidant property, developing into materials for aeroengines of new generation, can be used for making pneumatic plant, gas turbine blades, pneumatic plant stator windsheild, out frame and the casting of other complex-shaped large sizes and forging parts, substitute heavy nickel base superalloy with part, but loss of weight about 50%.γ-TiAl base alloy is for the manufacture of the turbo-supercharger of motor car engine, air valve etc.At present, China and each industrial country of the world are all conducting a research energetically, but the alloy species of practical application seldom.
From titanium aluminum binary Phase Diagram Analysis, when Al content was higher than 51at%, solidifying route in the titanium aluminum alloy castingprocesses was that γ solidifies mutually, and the titanium aluminum alloy after solidifying is in the γ single phase region.The non-constant of room temperature unit elongation of single-phase γ-TiAl, reason are that a lot of dislocations are not movable under single-phase γ-TiAl room temperature, and main slip dislocation is by fault dipole pinning.And α
2+ γ two-phase structure obviously is better than single-phase γ-TiAl on unit elongation and intensity, reason is α
2Absorb oxygen, thereby reduced the oxygen level among the γ, be beneficial to dislocation glide.
α solidifies route research much mutually in the titanium aluminum alloy preparation process in early days.Titanium aluminum binary phasor shows, when Al content is higher than 49.4 at%, when being lower than 51at%, the route that solidifies of Ti-Al alloy material is that α solidifies mutually, and it is as follows that α solidifies route mutually: the L(liquid phase) → and L+ α → α → α+γ → γ → α
2+ γ, room temperature undertissue are α
2+ γ.At first generate solid phase α when L cools off mutually in the process of setting, alpha-crystal will preferentially generate along its c-axis, thereby form obvious styloid feature, and the γ lamella of follow-up formation is perpendicular to α phase c-axis direction, it is the styloid direction of growth, the obvious dentrite tissue of final formation, thus the homogeneity of rear cast properties is solidified in impact.
Titanium-aluminum binary alloy phase diagram, when Al content when 44.8-49.4 at % is interval, in the gamma-TiAl alloy process of setting Peritectic Reaction will occur: L+ β → α.When Al content was positioned at 44.8-47.0%, Peritectic Reaction was incomplete, solidified route to be: L → L+ β → β+α → α → α+γ → α
2+ γ; When Al content was positioned at 47.0-49.4%, Peritectic Reaction was incomplete, solidified route to be: L → L+ β → L+ α → α → α+γ → γ → α
2+ γ.When Al content was 47.0%, Peritectic Reaction was carried out fully, solidified route and was: L → L+ β → α → α+γ → γ → α
2+ γ.Contain in the titanium aluminum alloy process of setting of Peritectic Reaction, Peritectic Reaction occurs in β phase and liquid interface place.Peritectic Reaction carries out can affecting to a certain extent when incomplete the homogeneity of material composition.Both at home and abroad through studying for many years and test, can be in practical application through the gamma-TiAl alloy of Peritectic Reaction, but it is poor through the gamma-TiAl alloy that β solidifies mutually to solidify the homogeneity of rear casting composition.
When Al content less than 44.8 at %, Ti-Al alloy material is that β solidifies mutually, solidifies route and is: L → L+ β → β → β+α → α → α+γ → α
2+ γ.β solidifies mutually and has best homogeneity of ingredients; In the β phase process of setting, owing to can form the α variant of 12 complete different directions in the β crystal, finally obtain being orientated diverse lath group, organize anisotropy very little after solidifying, each position its mechanical properties is consistent.But cross when low when Al content, organize α after causing solidifying
2α among the+γ
2Phase content is too high, affects the resistance to elevated temperatures of material.In gamma-TiAl alloy, add an amount of beta stable element such as Nb, Zr, Hf, the β phase region in the Ti-Al alloy phase diagram is moved right, thereby realize that β solidifies mutually.
Patent US6051084 points out that Nb can greatly improve the antioxidant property of titanium aluminum alloy, puies forward heavy alloyed hot strength and creep property, and alloy all has preferably antioxidant property when Nb content is 6 ~ 10%.Professor R.Yang of metal institute of the Chinese Academy of Sciences etc., " Alloy development and shell mould casting of gamma TiAl " (Journal of materials processing technology[J], 2003, studied 2 at %Nb, 5 at %Nb, 8 at %Nb 135:179-188) respectively on the impact of gamma-TiAl alloy antioxidant property and thermal fatigue resistance, better when antioxidant property, thermal fatigue resistance are than 8 at %Nb when drawing Nb content and being 5 at %; The titanium aluminum alloy thermal fatigue resistance is best when Nb content is 2 at %.
Patent US6294132 points out that Ni can improve the creep resistance of β phase, increases the friction of alloy inside and improve anti-seismic performance; Si can improve hot strength and the creep strength of titanium aluminum alloy, and can carry heavy alloyed antioxidant property.
Low Nb(is generally 1-3at%Nb) high temperature creep property and the high temperature oxidation resistance of Ti-Al alloy material be very poor, particularly when temperature during 850 ℃-950 ℃ long-time application the material surface oxidation serious, therefore, low Nb titanium aluminum alloy is not suitable for preparing the long-time component of using under 850-950 ℃ of hot environment usually.
Summary of the invention
Technical problem to be solved by this invention provides the excellent titanium aluminium base alloy that is fit to casting of a kind of high-temperature oxidation resistant creep property, be novel low Nb Ti-Al alloy material, on the basis of original low Nb Ti-Al alloy material, by lot of experiments research and data analysis, the alloying elements such as Mo, Si, C have been added in combination innovatively, and novel material present material both at home and abroad aspect much has obvious advantage.Mo, Si element are conducive to improve the high-temperature oxidation resistance of material; Si, C are conducive to improve the high temperature creep property of material simultaneously.Material castability of the present invention is excellent, is fit to be applied to the long-time component of using under the 850-950 ℃ of hot environment, such as the turibine rotor of turbosupercharger of car engine.Titanium aluminum surface need not to carry out chemical treatment, thermospray, the antioxidant property that improves material such as ion implantation usually under this temperature.
For the purpose that realizes solving the problems of the technologies described above, the present invention has adopted following technical scheme:
The excellent titanium aluminium base alloy that is fit to casting of a kind of high-temperature oxidation resistant creep property of the present invention, belong to gamma-TiAl alloy, specific chemical composition and atomic percent consist of: in Al:44.0 ~ 48.0 at%, Nb:1.0 ~ 3.0 at%, Mo:0.1-3.0at%, Si and the C element wherein one or both, Si:0-0.8 at% wherein, C:0-0.6 at%, and the total amount of Si and C element is 0.1-0.9 at%, and all the other are Ti and inevitable impurity element.
More specifically preferred, specific chemical composition and atomic percent form can for:
1）Ti-(44.0~48.0?)Al-(1.0~3.0)Nb-(0.1-3.0)Mo-(0.1-0.8)Si；
2）Ti-(44.0~48.0?)Al-(1.0~3.0)Nb-(0.1-3.0)Mo-(0.1-0.6)C；
3) total amount of Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.8) Si-(0.1-0.6) C, and Si and C element is 0.2-0.9 at%.
Above-mentioned high temperature resistant titanium and aluminum based alloy, preferred chemical ingredients mass percent form: Al is 46.0-48.0 at% preferably, more preferably 47 at%; The preferred 2.0-3.0 at% of Nb, more preferably 2.0 at%; Mo can preferred 1.0 ~ 2.0 at%, more preferably 1.0 at%.
For the alloy of Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.8) Si, Si is 0.2-0.6 at% preferably, more preferably 0.4 at%.
For Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.6) C, C is 0.2-0.5 at% preferably, more preferably 0.3 at%.
For the C alloy of Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.8) Si-(0.1-0.6), the total amount of Si and C element is 0.4-0.9 at%, Si is 0.2-0.6 at% preferably, more preferably 0.4 at%; C is 0.2-0.5 at% preferably, more preferably 0.3 at%.
These technical schemes comprise that preferred each element mass percent and preferred each element mass percent also can make up mutually or combination, thereby reach better technique effect.
The antioxidant property that is conducive to improve material by adding an amount of Mo improves the room temperature unit elongation simultaneously.When Mo content surpass the patent of invention material upper in limited time, the casting fluidity of material can significantly be reduced, the room temperature unit elongation worsens.
Add the casting fluidity energy that an amount of Si can improve material, improve simultaneously creep strength and the antioxidant property of titanium aluminum alloy, but the casting fluidity of material can significantly reduce when the Si too high levels, and Si content is crossed and low then can be improved not obvious to the casting fluidity of material.
This patent material has been broken and the C element has been considered as impurity element in titanium, titanium alloy and the titanium aluminum alloy industry, can not be as the traditional concept of alloying element, repeatedly test by reality, add an amount of C element as alloying element, the remarkable lamellar spacing of refinement material, improve the Properties of High Temperature Creep of material, improve room temperature, hot strength and the hardness of material.But prescribe a time limit above upper when C content, the casting fluidity of material can significantly reduce.
Titanium aluminum of the present invention all adopts titanium sponge, pure Al, AlNb50 alloy, AlMo60, AlSi10 alloy, pure C powder as raw material, melting and the turbine formwork of casting in vacuum induction furnace.Casting with the melting method of titanium aluminium ingot casting is: at first be evacuated to 3.5Pa, the starting material of Novel Titanium aluminum alloy materials are carried out the argon filling melting, argon pressure is 60000 Pa, and the continuation stirring was 2 minutes after all fusing was finished, titanium aluminum alloy ingot casting melt back 2 times.
The casting process of turbine formwork is: casting turbine formwork after 2 minutes was stirred in continuation after forvacuum degree 3.5Pa, titanium aluminium ingot casting all melted and finish.
By adopting technique scheme, the present invention has following beneficial effect:
A kind of titanium aluminium base alloy material provided by the invention, this alloy belongs to gamma-TiAl alloy, and existing good high-temperature behavior has again good casting fluidity, is fit to the casting of thin-walled parts, such as the turibine rotor of turbosupercharger of car engine.Its life-time service temperature is 850-950 ℃ of temperature, and titanium aluminium surface need not to carry out chemical treatment, thermospray, the antioxidant property that improves material such as ion implantation under this temperature.Be particularly suitable for casting use temperature at the petrol engine booster turbine rotor of working below 900-950 ℃, have huge market outlook.
Embodiment
Titanium aluminum of the present invention all adopts titanium sponge, pure Al, AlNb50 alloy, AlMo60, AlSi10 alloy, pure C powder as raw material, prepares burden melting and the turbine formwork of casting in vacuum induction furnace by composition and the content requirement of embodiment 1--embodiment 9.Casting with the melting method of titanium aluminium ingot casting is: at first be evacuated to 3.5Pa, the starting material of Novel Titanium aluminum alloy materials are carried out the argon filling melting, argon pressure is 60000 Pa, and the continuation stirring was 2 minutes after all fusing was finished, titanium aluminum alloy ingot casting melt back 2 times.The casting process of turbine formwork is: casting turbine formwork after 2 minutes was stirred in continuation after forvacuum degree 3.5Pa, titanium aluminium ingot casting all melted and finish.
The test-results of embodiment 1--embodiment 9 is as shown in the table.
* remarks: the casting turbine: point of blade thickness is about 0.4mm, and turbine diameter 40mm tests 20 of number of turbines at every turn.
Claims (9)
1. the excellent titanium aluminium base alloy that is fit to casting of a high-temperature oxidation resistant creep property, it is characterized in that: belong to gamma-TiAl alloy, specific chemical composition and atomic percent consist of: in Al:44.0 ~ 48.0 at%, Nb:1.0 ~ 3.0 at%, Mo:0.1-3.0at%, Si and the C element wherein one or both, Si:0-0.8 at% wherein, C:0-0.6 at%, and the total amount of Si and C element is 0.1-0.9 at%, and all the other are Ti and inevitable impurity element.
2. described titanium aluminium base alloy according to claim 1, it is characterized in that: the atomic percent of alloy consists of: Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.8) Si.
3. described titanium aluminium base alloy according to claim 1, it is characterized in that: the atomic percent of alloy consists of: Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.6) C.
4. described titanium aluminium base alloy according to claim 1, it is characterized in that: the atomic percent of alloy consists of: Ti-(44.0 ~ 48.0) Al-(1.0 ~ 3.0) Nb-(0.1-3.0) Mo-(0.1-0.8) Si-(0.1-0.6) C, and Si and C total amount are 0.2-0.9 at%.
5. according to claim 2,3 or 4 each described titanium aluminium base alloys, it is characterized in that: the atomic percent of alloy consists of: Al is 46.0-48.0 at%; Nb is 2.0-3.0 at%; Mo is 1.0 ~ 2.0 at%.
6. described titanium aluminium base alloy according to claim 2, it is characterized in that: the atomic percent of alloy consists of: Si is 0.2-0.6 at%.
7. described titanium aluminium base alloy according to claim 3, it is characterized in that: the atomic percent of alloy consists of: C is 0.2-0.5 at%.
8. described titanium aluminium base alloy according to claim 4, it is characterized in that: the atomic percent of alloy consists of: Si is 0.2-0.6 at%, C is 0.2-0.5 at%.
9. described titanium aluminium base alloy according to claim 8, it is characterized in that: the atomic percent of alloy consists of:, Si is 0.4 at%, C is 0.3 at%.
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| CN104878452A (en) * | 2015-05-13 | 2015-09-02 | 南京理工大学 | High-temperature high-strength TiAl-Nb monocrystal and preparation method thereof |
| CN104532061A (en) * | 2014-12-26 | 2015-04-22 | 北京科技大学 | High-temperature-resistant aluminum titanium oxide alloy and preparation method thereof |
| CN108977690B (en) * | 2018-07-31 | 2020-01-31 | 河北工业大学 | Sapphire whisker toughened TiAlN NbMo alloy composite material and preparation method thereof |
| JP2021121690A (en) * | 2020-01-31 | 2021-08-26 | 三菱重工航空エンジン株式会社 | TiAl-BASED ALLOY AND MANUFACTURING METHOD THEREOF |
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