CN105838923A - High-strength and high-plasticity titanium alloy with resistance to high-temperature oxidation at 800 DEG C - Google Patents

High-strength and high-plasticity titanium alloy with resistance to high-temperature oxidation at 800 DEG C Download PDF

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CN105838923A
CN105838923A CN201610379486.3A CN201610379486A CN105838923A CN 105838923 A CN105838923 A CN 105838923A CN 201610379486 A CN201610379486 A CN 201610379486A CN 105838923 A CN105838923 A CN 105838923A
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titanium alloy
temperature
strength
plasticity
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CN105838923B (en
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王清
董闯
王英敏
羌建兵
车晋达
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Dalian University of Technology
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

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  • Investigating And Analyzing Materials By Characteristic Methods (AREA)
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Abstract

The invention provides a high-strength and high-plasticity titanium alloy with resistance to high-temperature oxidation at 800 DEG C and belongs to the technical field of novel materials. The high-strength and high-plasticity titanium alloy comprises the following elements: Ti, Al, Sn, Zr, Hf, Mo, Ta, Nb and Si, wherein the alloy comprises the following components in percentage by weight: 5.7-6% of Al, 2.7-3% of Sn, 3.5-6.9% of Zr and Hf, 0.2-0.9% of Mo, Nb and Ta, 0.3-0.4% of Si and the balance of Ti. The high-strength and high-plasticity titanium alloy has the advantages that the addition content ratio of the component elements of the titanium alloy is reasonable due to alloy design, the alloy prepared on the basis of ensuring that the Ti alloy has single HCP-alpha phase structure has excellent resistance to high-temperature oxidation and excellent comprehensive mechanical property at 800 DEG C, and the titanium alloy is a low-cost aerospace engine material.

Description

A kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations
Technical field
The invention belongs to new material technology field, relate to a kind of anti-800 DEG C of high-temperature oxydations, high anti-corrosion and there is excellence The Aero-Space electromotor high-temperature titanium alloy structural material of comprehensive mechanical property.
Background technology
High temperature nearly α-Ti alloy has that density is little, high temperature oxidation resistance is strong, corrosion resistance is strong and comprehensive mechanical property is excellent etc. Advantage, is the primary structural material of Aero-Space electromotor.High-temperature titanium alloy uses temperature along with Aeroengine Design requirement Constantly mentioning, currently used temperature is up to 600 DEG C, and table 1 lists the high temperatures typical titanium alloy board using temperature more than 500 DEG C Number and composition, it can be seen that for guaranteeing Ti alloy usage performance at high temperature, it usually needs add multiple trace element and carry out Alloying, such as Al, Sn, Zr, Mo, Si and Ta etc. so that alloy exists a small amount of BCC-β phase on HCP-αsolidsolution matrix.The most It is important that, it is necessary to make the alloy element Proper Match of multiple common interpolation, to ensure the Stability Analysis of Structures of high temperature Ti alloy Property.But high-temperature titanium alloy can produce α in the case of high temperature prolonged heat exposure2-Ti3Al brittlement phase, will significantly reduce the plasticity of alloy And high high-temp stability, therefore the structural stability of high-temperature titanium alloy and non-oxidizability are that restriction alloy uses temperature two Essential condition.
High-temperature titanium alloy uses temperature to be only 600 DEG C at present, for using the higher working environment of temperature can only use it Its high-temperature material or use high temperature coating, be unfavorable for structural member loss of weight.The trade mark titanium alloy listed in table 1 still cannot meet more (> 600 DEG C under high-temperature) the aerospace field requirement to material at high temperature high-strength plasticity.Therefore find and use temperature higher than 600 Aerospace field development will be played vital effect by the titanium alloy more than DEG C.
The table 1 high temperatures typical titanium alloy trade mark and alloying component
Summary of the invention
It is an object of the invention to not can exceed that the deficiency of 600 DEG C for high-temperature titanium alloy existing use temperature, it is provided that a kind of Anti-800 DEG C of high-temperature oxydations, high anti-corrosion and there is the Aero-Space electromotor high-temperature titanium alloy of excellent comprehensive mechanical property tie Structure material.
The technical solution used in the present invention is: the high-strength plasticity titanium alloy of a kind of anti-800 DEG C of high-temperature oxydations, this high-strength plasticity Titanium alloy includes Ti, Al, Sn, Zr, Hf, Mo, Ta, Nb and Si element, and the percentage by weight of its alloying component is respectively, Al:5.7 ～6%, Sn:2.7～3%, Zr+Hf:3.5～6.9%, Mo+Nb+Ta:0.2～0.9%, Si:0.3～0.4%, surplus is Ti。
The design realizing technique scheme is: utilize applicant's " cluster+connection atom " structural model to design Ti- Al-Sn-Zr-Hf-Mo-Ta-Nb-Si alloying component.Solid solution can be tied by " cluster+connection atom " structural model from atom chemistry Structure regard as by cluster and connect atom two parts constitute, cluster empirical formula is [cluster] (connection atom)x.High-temperature titanium alloy parent phase For the β phase of BCC structure, therefore using BCC structure cluster models, in the model, 14 Zr atoms occupy the first shell and are formed CN14 polyhedron cluster, other alloy element occupy-place principle in cluster formula is: with the negative heat of mixing that Ti has maximum Element al occupies cluster heart portion, has strong reciprocal action, forms [Al-Ti14] cluster；Sn, Mo, Ta, Nb, Si easily divide with Ti atom From, there is weak anastomosis, as Cluster Structures model connects atom；With element Zr, Hf that Ti enthalpy of mixing is 0, for Ti's Constituent element of the same clan, the Ti on alternative cluster shell.Therefore in Ti-Al-Sn-Zr-Hf-Mo-Ta-Nb-Si system alloy, formation Cluster composition formula is [Al-(Ti, Zr, Hf)14]M1(M is Al, Sn, Mo, Ta, Nb, Si).Become according to this empirical formula design alloy Point, it is then converted into percentage by weight.The principle of design is to ensure that each alloy element adds the optimal proportion of content, to ensure Alloy embodies strong anti-oxidation performance and comprehensive mechanical property on BCC Cluster Structures model.
The composition alloy of the present invention uses high-purity constituent element element alloying component by weight percentage to carry out proportioning；Then profit Under Ar gas shielded, the mixture of proportioning is carried out repeatedly melting with non-consumable arc-melting furnace, to obtain the uniform alloy of composition Ingot, then utilizes copper mold rapid cooling technique alloy pig to be prepared as the alloy bar of a diameter of 6mm, as non-oxidizability, mechanics Performance, corrosion resisting property experiment test sample；Utilize XRD (Cu KαRadiation, λ=0.15406nm) detection alloy structure；Utilize aobvious The hardness of micro-Vickers test titanium alloy；Utilize MTS testing machine test room temperature and mechanical behavior under high temperature；Muffle furnace is utilized to survey Examination antioxygenic property；Utilize Gamry electrochemical workstation beta alloy corrosion resisting property.Thereby determine that out the present invention has anti- 800 DEG C of high-temperature oxydations, high corrosion-resistant and the Aero-Space electromotor high-temperature titanium alloy structural material of excellent comprehensive mechanical property, The percentage by weight of its alloying component is, Al:5.7～6%, Sn:2.7～3%, Zr+Hf:3.5～6.9%, Mo+Nb+Ta: 0.2～0.9%, Si:0.3～0.4%.Material performance index is: hardness HV=320-380kgf mm-2, mechanical properties σb=990-1200MPa, 650 DEG C of hot strengths σb=550-600MPa, 650 DEG C of plasticity ε=30-60%, 800 DEG C of oxidation 100h Rear oxidation weightening finish G+=1.5～6mg/cm2, from corrosion potentials E in 3.5%NaCl solutioncorr=-0.3～-0.2V, corrosion speed Rate R=1.5～5 μm/a.
Compared with prior art, it is an advantage of the current invention that: the present invention is to close according to a kind of cluster that we develop voluntarily Gold method for designing designs and has developed the high-strength plasticity titanium alloy of a kind of anti-800 DEG C of high-temperature oxydations, by alloy design really Protect the alloying element content proportioning added and reach optimum, shield the compositions, method that the experience of " cooking formula " at present is loaded down with trivial details, tool There is the guiding of design of material；Thus obtained titanium alloy has high structural stability, 800 DEG C of excellent high-temperature oxidation resistant energy Power and the room temperature of excellence and high temperature comprehensive mechanical property and corrosion resisting property, its typical performance indicators is: hardness HV=320- 380kgf·mm-2, mechanical properties σb=990-1200MPa, 650 DEG C of hot strengths σb=550-600MPa, 650 DEG C of plasticity ε=30-60%, 800 DEG C of oxidation 100h rear oxidation weightening finish G+=1.5～6mg/cm2, from corrosion potentials in 3.5%NaCl solution Ecorr=-0.3～-0.2VV, corrosion rate R=1.5～5 μm/a.
The method have the benefit that on the basis of 1. ensureing that Ti alloy has single HCP-α phase structure, it is thus achieved that Ti-Al-Sn- Zr-Hf-Mo-Ta-Nb-Si alloy also has excellent high temperature oxidation resistance and comprehensive mechanical property；2. designed by alloy, The constituent element element making titanium alloy adds content reasonable mixture ratio, thus realizes alloy and have the high temperature resistance oxygen of excellence at 800 DEG C The powerful plasticity of height under change ability and high temperature；3. the titanium alloy developed, while having Good All-around Property, is a kind of low Cost Aero-Space engine material.
Detailed description of the invention
The detailed description of the invention of the present invention is described in detail below in conjunction with technical scheme.
Embodiment 1:Ti86.47Al6.01Sn2.82Zr3.61Ta0.72Si0.37Alloy
Step one: prepared by alloy
Ti86.47Al6.01Sn2.82Zr3.61Ta0.72Si0.37Alloy, this composition is derived from cluster formula [Al-(Ti13.7Zr0.3)] (Al0.69Sn0.18Si0.1Ta0.03).Ti, Al, Sn, Zr, Ta, Si simple metal is carried out according to given weight alloy percent composition Dispensing；Compound is placed in the water jacketed copper crucible of arc-melting furnace, uses non-consumable arc melting method under the protection of argon Carry out melting, such melt back 3 times, obtain the uniform alloy pig of composition；Then uniform for melting alloy pig is finally melted, And utilize copper mold technique to be sucked in cylindrical, copper model cavity by melt, obtain the bar of φ 6mm, φ 6mm alloy bar is existed Shrend after 950 DEG C of solution treatment insulation 1h, and carry out Ageing Treatment insulation 6h at 560 DEG C.
Step 2: alloy structure and performance test
Utilize XRD to detect alloy structure, be defined as single HCP-αsolidsolution structure；Utilize micro Vickers, Muffle Stove, MTS testing machine and Gamry electrochemical workstation test its performance parameter, are respectively as follows: hardness HV=354kgf mm-2, 800 DEG C oxidation 100h rear oxidation weightening finish G+=1.8mg/cm2, mechanical properties σb=990MPa, 650 DEG C of hot strengths σb= 560MPa, 650 DEG C of plasticity ε=38%, from corrosion potentials E in 3.5%NaCl solutioncorr=-0.26V, corrosion rate R= 3.0μm/a。
Embodiment 2:Ti86.64Al6.02Sn2.82Zr3.61Ta0.36Nb0.18Si0.37Alloy
Step one: prepared by alloy
Ti86.64Al6.02Sn2.82Zr3.61Ta0.36Nb0.18Si0.37Alloy, [Al-(Ti13.7Zr0.3)](Al0.69Sn0.18Si0.1- Ta0.015Nb0.015).With the step one in embodiment one.
Step 2: alloy structure and performance test
Utilize XRD to detect alloy structure, be defined as single HCP-αsolidsolution structure；Utilize micro Vickers, Muffle Stove, MTS testing machine and Gamry electrochemical workstation test its performance parameter, are respectively as follows: hardness HV=378kgf mm-2, 800 DEG C oxidation 100h rear oxidation weightening finish G+=3.9mg/cm2, mechanical properties σb=1032MPa, 650 DEG C of hot strengths σb= 580MPa, 650 DEG C of plasticity ε %=51%, from corrosion potentials E in 3.5%NaCl solutioncorr=-0.23V, corrosion rate R= 2.1μm/a。
Embodiment 3:Ti86.67Al6.03Sn2.82Zr3.62Mo0.13Ta0.24Nb0.12Si0.37Alloy
Step one: prepared by alloy
Ti86.67Al6.03Sn2.82Zr3.62Mo0.13Ta0.24Nb0.12Si0.37Alloy, [Al-(Ti13.7Zr0.3)] (Al0.69Sn0.18-Si0.1Mo0.01Ta0.01Nb0.01).With the step one in embodiment one.
Step 2: alloy structure and performance test
Utilize XRD to detect alloy structure, be defined as single HCP-αsolidsolution structure；Utilize micro Vickers, Muffle Stove, MTS testing machine and Gamry electrochemical workstation test its performance parameter, are respectively as follows: hardness HV=376kgf mm-2, 800 DEG C oxidation 100h rear oxidation weightening finish G+=5.6mg/cm2, mechanical properties σb=1190MPa, 650 DEG C of hot strengths σb= 580MPa, 650 DEG C of plasticity ε %=60%, from corrosion potentials E in 3.5%NaCl solutioncorr=-0.27V, corrosion rate R= 1.7μm/a。
Embodiment 4:Ti83.77Al5.82Sn2.73Hf6.84Mo0.12Ta0.23Nb0.12Si0.36Alloy
Step one: prepared by alloy
Ti83.77Al5.82Sn2.73Hf6.84Mo0.12Ta0.23Nb0.12Si0.36Alloy, [Al-(Ti13.7Hf0.3)] (Al0.69Sn0.18-Si0.1Mo0.01Ta0.01Nb0.01).With the step one in embodiment one.
Step 2: alloy structure and performance test
Utilize XRD to detect alloy structure, be defined as single HCP-αsolidsolution structure；Utilize micro Vickers, Muffle Stove, MTS testing machine and Gamry electrochemical workstation test its performance parameter, are respectively as follows: hardness HV=323kgf mm-2, 800 DEG C oxidation 100h rear oxidation weightening finish G+=2.2mg/cm2, mechanical properties σb=995MPa, 650 DEG C of hot strengths σb= 570MPa, 650 DEG C of plasticity ε %=53%, from corrosion potentials E in 3.5%NaCl solutioncorr=-0.22V, corrosion rate R= 2.7μm/a。
Embodiment 5:Ti85.19Al5.92Sn2.78Zr1.79Hf3.48Mo0.12Ta0.24Nb0.12Si0.36Alloy
Step one: prepared by alloy
Ti85.19Al5.92Sn2.78Zr1.79Hf3.48Mo0.12Ta0.24Nb0.12Si0.36Alloy, [Al- (Ti13.7Zr0.15Hf0.15)]-(Al0.69Sn0.18Si0.1Mo0.01Ta0.01Nb0.01).With the step one in embodiment one.
Step 2: alloy structure and performance test
Utilize XRD to detect alloy structure, be defined as single HCP-αsolidsolution structure；Utilize micro Vickers, Muffle Stove and Gamry electrochemical workstation test its performance parameter, are respectively as follows: hardness HV=365kgf mm-2, 800 DEG C of oxidation 100h Rear oxidation weightening finish G+=4.6mg/cm2, mechanical properties σb=1200MPa, 650 DEG C of hot strengths σb=600MPa, 650 DEG C Plasticity ε %=48%, from corrosion potentials-0.24V in 3.5%NaCl solution, corrosion rate R=4.5 μm/a.

Claims (1)

1. the high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations, it is characterised in that: this high-strength plasticity titanium alloy include Ti, Al, Sn, Zr, Hf, Mo, Ta, Nb and Si element, the percentage by weight of its alloying component is, Al:5.7～6%, Sn:2.7～ 3%, Zr+Hf:3.5～6.9%, Mo+Nb+Ta:0.2～0.9%, Si:0.3～0.4%, surplus is Ti.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058804A (en) * 2017-04-19 2017-08-18 中国航发北京航空材料研究院 A kind of high-temperature titanium alloy of high heat-intensity
CN112322936A (en) * 2020-11-05 2021-02-05 北京航空航天大学 Anti-oxidation high-temperature titanium alloy and preparation method thereof
CN113046595A (en) * 2021-03-17 2021-06-29 大连理工大学 High-strength and high-toughness titanium alloy with good additive manufacturing forming performance and used at high temperature of 600 DEG C

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CN101768684A (en) * 2008-12-26 2010-07-07 北京有色金属研究总院 High temperature titanium alloy and surface modification method thereof
CN104561656A (en) * 2014-12-16 2015-04-29 中国航空工业集团公司北京航空材料研究院 High-temperature titanium alloy

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JPH05163542A (en) * 1991-12-13 1993-06-29 Sumitomo Metal Ind Ltd Heat-resistant titanium alloy
JPH08120373A (en) * 1994-08-22 1996-05-14 Sumitomo Metal Ind Ltd High creep strength titanium alloy and its production
JPH0931572A (en) * 1995-07-21 1997-02-04 Sumitomo Metal Ind Ltd Heat resistant titanium alloy excellent in high temperature fatigue strength
CN1310769A (en) * 1998-07-21 2001-08-29 株式会社丰田中央研究所 Titanium-based composition material, method for producing the same and engine valve
CN101768684A (en) * 2008-12-26 2010-07-07 北京有色金属研究总院 High temperature titanium alloy and surface modification method thereof
CN104561656A (en) * 2014-12-16 2015-04-29 中国航空工业集团公司北京航空材料研究院 High-temperature titanium alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107058804A (en) * 2017-04-19 2017-08-18 中国航发北京航空材料研究院 A kind of high-temperature titanium alloy of high heat-intensity
CN112322936A (en) * 2020-11-05 2021-02-05 北京航空航天大学 Anti-oxidation high-temperature titanium alloy and preparation method thereof
CN112322936B (en) * 2020-11-05 2022-03-04 北京航空航天大学 Anti-oxidation high-temperature titanium alloy and preparation method thereof
CN113046595A (en) * 2021-03-17 2021-06-29 大连理工大学 High-strength and high-toughness titanium alloy with good additive manufacturing forming performance and used at high temperature of 600 DEG C
CN113046595B (en) * 2021-03-17 2022-05-10 大连理工大学 High-strength and high-toughness titanium alloy with good additive manufacturing forming performance and used at high temperature of 600 DEG C

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