CN105838923B - A kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations - Google Patents

A kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations Download PDF

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CN105838923B
CN105838923B CN201610379486.3A CN201610379486A CN105838923B CN 105838923 B CN105838923 B CN 105838923B CN 201610379486 A CN201610379486 A CN 201610379486A CN 105838923 B CN105838923 B CN 105838923B
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temperature
titanium alloy
corrosion
cluster
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CN105838923A (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

Abstract

The present invention provides a kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations, belongs to new material technology field, and it includes Ti, Al, Sn, Zr, Hf, Mo, Ta, Nb and Si element, and 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.The present invention has the beneficial effect that and designed by alloy, the constituent element element of titanium alloy is set to add content reasonable mixture ratio, on the basis of ensureing that Ti alloys have single HCP α phase structures, the alloy of acquisition has excellent oxidation-resistance property and excellent comprehensive mechanical property at 800 DEG C, is a kind of Low-cost Aviation space flight 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, it is related to a kind of anti-800 DEG C of high-temperature oxydations, high anti-corrosion and with excellent The Aero-Space engine high-temperature titanium alloy structural material of comprehensive mechanical property.
Background technology
Nearly α-Ti the alloys of high temperature have density is small, 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 engine.High-temperature titanium alloy temperature in use is required with Aeroengine Design Constantly mention, current temperature in use is up to 600 DEG C, table 1 lists the high temperatures typical titanium alloy board of more than 500 DEG C of temperature in use Number and composition, it can be seen that to ensure the usage performance of Ti alloys at high temperature, it usually needs add multiple trace elements and carry out Alloying, such as Al, Sn, Zr, Mo, Si and Ta so that alloy has a small amount of BCC- β phases on HCP- αsolidsolution matrixes.The most It is important that, it is necessary to so that multiple alloy element Proper Matchs added jointly, to ensure the Stability Analysis of Structures of high temperature Ti alloys Property.But high-temperature titanium alloy can produce α in the case of high temperature prolonged heat exposure2-Ti3Al brittlement phases, will significantly reduce the plasticity of alloy And high high-temp stability, therefore the structural stability and inoxidizability of high-temperature titanium alloy are to restrict alloy temperature in use two most Essential condition.
Current high-temperature titanium alloy temperature in use is only 600 DEG C, and it can only be used for the higher working environment of temperature in use Its high-temperature material uses high temperature coating, is unfavorable for structural member loss of weight.The trade mark titanium alloy listed in table 1 can not still be met more Under high-temperature (>600 DEG C) requirement of the aerospace field to material at high temperature high-strength plasticity.Therefore find temperature in use and be higher than 600 Titanium alloy more than DEG C will play vital effect to aerospace field development.
The high temperatures typical titanium alloy trade mark of table 1 and alloying component
The content of the invention
The purpose of the present invention is that there is provided one kind for not enough no more than 600 DEG C of the existing temperature in use of high-temperature titanium alloy Anti- 800 DEG C of high-temperature oxydations, high anti-corrosion and with excellent comprehensive mechanical property Aero-Space engine high-temperature titanium alloy knot Structure material.
The technical solution adopted by the present invention is：A kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations, the 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。
Realizing the design of above-mentioned technical proposal is：Ti- is designed using " cluster+connection atom " structural model of applicant Al-Sn-Zr-Hf-Mo-Ta-Nb-Si alloying components." cluster+connection atom " structural model can be by solid solution knot from atom chemistry Structure is regarded as to be made up of cluster and connection atom two parts, and cluster empirical formula is [cluster] (connection atom)x.High-temperature titanium alloy parent phase For the β phases of BCC structures, therefore BCC structure cluster models are used, in the model, 14 Zr atoms occupy the first shell and formed CN14 polyhedron clusters, occupy-place principle of other alloy elements in cluster formula be：There is maximum negative heat of mixing with Ti Element al occupies cluster center portion, with strong reciprocation, forms [Al-Ti14] cluster；Sn, Mo, Ta, Nb, Si and Ti atom easily divide From with weak anastomosis, as connecting atom in cluster structure model；It is Ti's with element Zr, Hf that Ti enthalpy of mixing is 0 Ti on constituent element of the same clan, alternative cluster shell.Therefore in Ti-Al-Sn-Zr-Hf-Mo-Ta-Nb-Si system alloys, formation Cluster composition formula is [Al- (Ti, Zr, Hf)14]M1(M is Al, Sn, Mo, Ta, Nb, Si).According to this empirical formula design alloy into 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 structure models.
The composition alloy of the present invention is matched using high-purity constituent element element alloying component by weight percentage；Then it is sharp Multiple melting is carried out to the mixture of proportioning under Ar gas shieldeds with non-consumable arc-melting furnace, to obtain the uniform alloy of composition Alloy pig, is then prepared into a diameter of 6mm alloy bar by ingot using copper mold rapid cooling technique, as inoxidizability, mechanics Performance, corrosion resisting property experiment test sample；Utilize XRD (Cu KαRadiation, λ=0.15406nm) detection alloy structure；Using aobvious Micro- Vickers tests the hardness of titanium alloy；Normal temperature and mechanical behavior under high temperature are tested using MTS testing machines；Surveyed using Muffle furnace Try antioxygenic property；Utilize Gamry electrochemical workstation beta alloy corrosion resisting properties.Thereby determine that out to have in the present invention and resist The Aero-Space engine high-temperature titanium alloy structural material of 800 DEG C of high-temperature oxydations, high corrosion-resistant and 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=320-380kgfmm-2, mechanical properties σb=990-1200MPa, 650 DEG C of tensile strength σb=550-600MPa, 650 DEG C of plasticity ε=30-60%, 800 DEG C of oxidation 100h Rear oxidation weightening G+=1.5~6mg/cm2, the self-corrosion voltage E in 3.5%NaCl solutioncorr=-0.3~-0.2V, corrosion speed Rate R=1.5~5 μm/a.
Compared with prior art, the advantage of the invention is that：The present invention is closed according to a kind of cluster that we voluntarily develop Golden design method designs and developed a kind of high-strength plasticity titanium alloy for resisting 800 DEG C of high-temperature oxydations, designs true by alloy The alloying element content proportioning for protecting addition is optimal, and shields the cumbersome compositions, method of the experience of current " cooking formula ", 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 excellent room temperature 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 tensile strength σb=550-600MPa, 650 DEG C of plasticity ε=30-60%, 800 DEG C of oxidation 100h rear oxidation weightenings G+=1.5~6mg/cm2, the self-corrosion voltage in 3.5%NaCl solution Ecorr=-0.3~-0.2VV, corrosion rate R=1.5~5 μm/a.
Beneficial effect of the present invention：1. on the basis of ensureing Ti alloys there is single HCP- α phase structures, the Ti-Al-Sn- of acquisition Zr-Hf-Mo-Ta-Nb-Si alloys simultaneously have excellent high temperature oxidation resistance and comprehensive mechanical property；2. designed by alloy, So that the constituent element element addition content reasonable mixture ratio of titanium alloy, so as to realize that alloy has excellent high temperature resistance oxygen at 800 DEG C High powerful plasticity under change ability and high temperature；3. the titanium alloy developed is a kind of low while with Good All-around Property Cost Aero-Space engine material.
Embodiment
Describe the embodiment of the present invention in detail below in conjunction with technical scheme.
Embodiment 1：Ti86.47Al6.01Sn2.82Zr3.61Ta0.72Si0.37Alloy
Step one：It is 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 are carried out according to given weight alloy percent composition Dispensing；Compound is placed in the water jacketed copper crucible of arc-melting furnace, using non-consumable arc melting method under the protection of argon gas Melting is carried out, such melt back 3 times obtains the uniform alloy pig of composition；Then the uniform alloy pig of melting is finally melted, And sucked melt in cylindrical, copper model cavity using copper mold technique, φ 6mm bar is obtained, φ 6mm alloy bars are existed Water quenching after 950 DEG C of solution treatment insulation 1h, and in 560 DEG C of progress Ageing Treatment insulation 6h.
Step 2：Alloy structure and performance test
Alloy structure is detected using XRD, is defined as single HCP- αsolidsolutions structure；Utilize micro Vickers, Muffle Stove, MTS testing machines and Gamry electrochemical workstations test its performance parameter, are respectively：Hardness HV=354kgfmm-2, 800 DEG C oxidation 100h rear oxidations weightening G+=1.8mg/cm2, mechanical properties σb=990MPa, 650 DEG C of tensile strength σb= 560MPa, 650 DEG C of plasticity ε=38%, the self-corrosion voltage 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：It is prepared by alloy
Ti86.64Al6.02Sn2.82Zr3.61Ta0.36Nb0.18Si0.37Alloy, [Al- (Ti13.7Zr0.3)](Al0.69Sn0.18Si0.1- Ta0.015Nb0.015).Step one in be the same as Example one.
Step 2：Alloy structure and performance test
Alloy structure is detected using XRD, is defined as single HCP- αsolidsolutions structure；Utilize micro Vickers, Muffle Stove, MTS testing machines and Gamry electrochemical workstations test its performance parameter, are respectively：Hardness HV=378kgfmm-2, 800 DEG C oxidation 100h rear oxidations weightening G+=3.9mg/cm2, mechanical properties σb=1032MPa, 650 DEG C of tensile strength σb= 580MPa, 650 DEG C of plasticity ε %=51%, the self-corrosion voltage 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：It is prepared by alloy
Ti86.67Al6.03Sn2.82Zr3.62Mo0.13Ta0.24Nb0.12Si0.37Alloy, [Al- (Ti13.7Zr0.3)] (Al0.69Sn0.18-Si0.1Mo0.01Ta0.01Nb0.01).Step one in be the same as Example one.
Step 2：Alloy structure and performance test
Alloy structure is detected using XRD, is defined as single HCP- αsolidsolutions structure；Utilize micro Vickers, Muffle Stove, MTS testing machines and Gamry electrochemical workstations test its performance parameter, are respectively：Hardness HV=376kgfmm-2, 800 DEG C oxidation 100h rear oxidations weightening G+=5.6mg/cm2, mechanical properties σb=1190MPa, 650 DEG C of tensile strength σb= 580MPa, 650 DEG C of plasticity ε %=60%, the self-corrosion voltage 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：It is prepared by alloy
Ti83.77Al5.82Sn2.73Hf6.84Mo0.12Ta0.23Nb0.12Si0.36Alloy, [Al- (Ti13.7Hf0.3)] (Al0.69Sn0.18-Si0.1Mo0.01Ta0.01Nb0.01).Step one in be the same as Example one.
Step 2：Alloy structure and performance test
Alloy structure is detected using XRD, is defined as single HCP- αsolidsolutions structure；Utilize micro Vickers, Muffle Stove, MTS testing machines and Gamry electrochemical workstations test its performance parameter, are respectively：Hardness HV=323kgfmm-2, 800 DEG C oxidation 100h rear oxidations weightening G+=2.2mg/cm2, mechanical properties σb=995MPa, 650 DEG C of tensile strength σb= 570MPa, 650 DEG C of plasticity ε %=53%, the self-corrosion voltage 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：It is 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).Step one in be the same as Example one.
Step 2：Alloy structure and performance test
Alloy structure is detected using XRD, is defined as single HCP- αsolidsolutions structure；Utilize micro Vickers, Muffle Stove and Gamry electrochemical workstations test its performance parameter, are respectively：Hardness HV=365kgfmm-2, 800 DEG C of oxidation 100h Rear oxidation weightening G+=4.6mg/cm2, mechanical properties σb=1200MPa, 650 DEG C of tensile strength σb=600MPa, 650 DEG C Plasticity ε %=48%, the self-corrosion voltage -0.24V in 3.5%NaCl solution, R=4.5 μm of corrosion rate/a.

Claims (1)

1. a kind of high-strength plasticity titanium alloy of anti-800 DEG C of high-temperature oxydations, it is characterised in that：The 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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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
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
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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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

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