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WO2018199791A1 - Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température - Google Patents

Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température Download PDF

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Publication number
WO2018199791A1
WO2018199791A1 PCT/RU2017/000266 RU2017000266W WO2018199791A1 WO 2018199791 A1 WO2018199791 A1 WO 2018199791A1 RU 2017000266 W RU2017000266 W RU 2017000266W WO 2018199791 A1 WO2018199791 A1 WO 2018199791A1
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WO
WIPO (PCT)
Prior art keywords
spd
temperature
low
phase
sheet material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/RU2017/000266
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English (en)
Russian (ru)
Inventor
Михаил Оттович ЛЕДЕР
Игорь Юрьевич ПУЗАКОВ
Наталья Юрьевна ТАРЕНКОВА
Александр Владимирович БЕРЕСТОВ
Наталия Георгиевна МИТРОПОЛЬСКАЯ
Роберт Дэвид БРИГГС
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
VSMPO Avisma Corp PSC
Boeing Co
Original Assignee
VSMPO Avisma Corp PSC
Boeing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by VSMPO Avisma Corp PSC, Boeing Co filed Critical VSMPO Avisma Corp PSC
Priority to RU2017139320A priority Critical patent/RU2691434C2/ru
Priority to US16/607,592 priority patent/US20200149133A1/en
Priority to BR112019022330-4A priority patent/BR112019022330B1/pt
Priority to EP17907725.0A priority patent/EP3617335B1/fr
Priority to CA3062762A priority patent/CA3062762A1/fr
Priority to PCT/RU2017/000266 priority patent/WO2018199791A1/fr
Priority to CN201780091937.6A priority patent/CN111279003B/zh
Priority to JP2019558569A priority patent/JP7028893B2/ja
Publication of WO2018199791A1 publication Critical patent/WO2018199791A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • 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

Definitions

  • the invention relates to the field of sheet materials (semi-finished products) based on titanium alloys, which are suitable for manufacturing products by low-temperature superplastic deformation (SPD) at a temperature of 775 ° C, and can be used as a cheaper alternative to sheet semi-finished products, made - made of T.-6A1-4V alloy.
  • SPD superplastic deformation
  • superplastic deformation generally refers to a process in which a material (alloy) is superplastically deformed, exceeding the usual limit of plastic deformation (over 500%).
  • SPD can be performed with certain materials with superplastic properties in a limited range of temperatures and strain rates.
  • sheets of titanium alloys can usually be superplastically formed (deformed) in the temperature range of about (900-1010) ° C at a strain rate of about 3 ⁇ 10 "4 s " 1 .
  • SUBSTITUTE SHEET (RULE 26) the use of a layer enriched with oxygen (alpha layer) and the formation of scale, which improves the yield of products and eliminates the need for chemical etching. In addition to this, lower deformation temperatures can inhibit grain growth, while maintaining the benefits of having smaller grains after SPD molding operations.
  • the first approach is to develop a special thermomechanical treatment that creates small grains having sizes in the range of only 2 to 1 ⁇ m or less, which improves creep along the grain boundaries.
  • RF Patent jYs 2243833, IPC B21B1 / 38, publ. 10.01.2005 there is a known method of manufacturing sheets for deformation at a temperature lower than during conventional molding of products from material Ti-6A1-4V.
  • the second approach is to develop a new system of sheet materials from titanium alloys, which demonstrates the presence of superplasticity with larger grain sizes of the material due to:
  • TPP lower temperature polymorphic transformation
  • biphasic (a +) -titanium alloys belong to the class of alloys with a structural equivalent in terms of molybdenum [Mo] equiv. equal to from 2.5 to 10%.
  • Mo molybdenum
  • Such alloys are usually alloyed with aluminum and ⁇ stabilizers to fix the ⁇ phase.
  • the amount of ⁇ -phase can vary from 5 to 50%.
  • the mechanical properties vary over a fairly wide range.
  • a known method of manufacturing sheet semi-finished products from titanium alloys suitable for low-temperature superplastic deformation from VT6 alloy, an analog of Ti-6A1-4V alloy, (RF Patent K “2224047, IPC C22F1 / 18, B21BZ / 00, publ. 20.02. 2004).
  • the method allows the manufacture of sheet semi-finished products from titanium alloys with a homogeneous submicrocrystalline structure
  • SUBSTITUTE SHEET (RULE 26) (grain size less than 1 ⁇ m) suitable for low temperature superplastic deformation.
  • the method is expensive, low productivity and requires specialized equipment.
  • the Ti-6A1-4V alloy with a submicrocrystalline structure obtained by intensive plastic deformation (IPD) by the method of comprehensive forging and having superplastic properties is known.
  • the microstructure of the alloy is characterized by grains and subgrains of the a- and ⁇ -phases with an average size of 0.4 ⁇ m, a high level of internal stresses and elastic distortions of the crystal lattice, as evidenced by the inhomogeneous diffraction contrast and high density of dislocations in the electron-microscopic images of the structure.
  • S. Zherebtsov, G. Salishchev, R. Galeyev, K. Maekawa Mechanical properties of Ti-6A1-4V titanium alloy with submicrocrystalline structure produced by severe plastic deformation. // Materials Transactions. 2005; V. 46 (9 ): 2020-2025.
  • SUBSTITUTE SHEET (RULE 26)
  • the semi-finished sheet product with a thickness of ⁇ 3 mm obtained according to this patent is not suitable for industrial production due to the low stability of properties for SPD.
  • the reason is that the use of strength alloys as chemical composition regulators does not allow us to control the necessary optimal relationships between the content of alloying additives in the alloy and the necessary structural properties of the alloy during SPD operations in sheet semi-finished products.
  • Si and Zr are present in the alloy, which form silicides on the grain surface, which hinder intergranular sliding and lead to process instability.
  • the aim of the present invention is to obtain a sheet material based on an (a +) -titanium alloy having the properties of low-temperature superplastic deformation with a grain size of more than 2 ⁇ m.
  • This sheet material has stable properties and is a cheaper alternative to sheet semi-_ ⁇ apricots made of Ti-6Al-4Vc alloy with a smaller grain size.
  • the technical result achieved during the implementation of the invention is the production of titanium alloy sheets in which the chemical composition is optimally balanced with the production capabilities based on known standard technologies of the final product having the properties of low-temperature superplastic deformation.
  • the specified technical result is achieved by the fact that the sheet material for low-temperature superplastic deformation based on a titanium alloy containing wt.% 4,5-5, 5A1, 4,5-
  • the sheet material for low-temperature superplastic deformation has a structure with a grain size not exceeding 8 microns.
  • Sheet material for low-temperature superplastic deformation has superplastic properties at a temperature of 775 ⁇ 10 ° ⁇ .
  • Sheet material for low-temperature superplastic deformation at a temperature of 775 ⁇ 10 ° C has an ⁇ / ⁇ phase ratio from 0.9 to 1.1.
  • Sheet material for low-temperature superplastic deformation in which the number of alloying elements diffusing between the a and ⁇ phases in the SPD process is at least 0.5% and is determined by the following ratio:
  • Q is the number of diffusing alloying elements in the material during SPD, wt.%.
  • p is the number of alloying elements in the material
  • mod is the content of the alloying element in the ⁇ phase before SPD
  • wt.% is the content of the alloying element in the ⁇ phase after SPD
  • mass. % is the content of the alloying element in the ⁇ phase after SPD
  • the proposed sheet material has a complex of high technological and structural properties. This is achieved due to the optimal selection of alloying elements and their ratio in the alloy of the material.
  • a group of stabilizers is a group of stabilizers.
  • Aluminum which is used in almost all industrial alloys, is the most effective hardener, improving the strength and heat-resistant properties of titanium.
  • the aluminum content in the alloy is less than 4.5%, the required alloy strength is not achieved, when the content is more than 5.5%, an undesirable decrease in ductility and an increase in TIP occur.
  • Oxygen increases the temperature of the allotropic transformation
  • the group of ⁇ stabilizers that are represented in the present invention (V, Mo, Cr, Fe, Ni) are widely used in industrial alloys.
  • Vanadium in an amount of 4.5-5.5%, iron in an amount of 0.8-1, 5% and chromium in an amount of 0.1-0.5% increase the strength of the alloy and practically
  • molybdenum in the range of 0.1-1.0% ensures its complete solubility in the ⁇ -phase, which allows to obtain the necessary strength characteristics without reducing the plastic properties.
  • the proposed alloy contains iron in an amount of 1.0-1.5% and nickel in an amount of 0.1-0.5%, which are the most diffusion-mobile ⁇ -stabilizers that favorably affect the intergranular slip during SPD.
  • SUBSTITUTE SHEET leads to an increase in TPP, and, consequently, to an increase in the temperature of the realization of SPD.
  • the optimum temperature at which the superplastic properties of the claimed material are realized is 775 ⁇ 10 ° C. Exceeding this temperature leads to grain growth, and lower to a decrease in the intensity of diffusion processes, which complicates the SPD process.
  • the amount of diffusing alloying elements of the alloy between the a and ⁇ phases must be at least 0.5%. This is explained by the fact that the activation energy of grain boundary diffusion is less than the activation energy of bulk diffusion, and diffusion transfer of atoms occurs along grain boundaries. In those regions of grain boundaries that are subjected to normal tensile stress, the concentration of vacancies is increased. In areas in which compressive stress acts, their concentration is reduced: the resulting difference in concentrations causes directional diffusion of vacancies. Since the migration of vacancies occurs through exchange of places with atoms, the latter will move in the opposite direction, intensifying intergrain gliding.
  • FIG. 1 and 2 show the structure of the alloys in the initial state
  • FIG. 6 is a graph of changes in true stress at a degree of deformation of 0.2 and 1, 1 (in the longitudinal direction) depending on [Mo] eq.
  • SUBSTITUTE SHEET (RULE 26) As a material for the study used sheet semi-finished products with a thickness of 2 mm To obtain sheet materials, six experimental alloys of various chemical composition were melted, which are presented in table 1.
  • the average grain size of the phases has a certain tendency to increase with increasing [Mo] eq and lies in the range of 2.8-3.8 ⁇ m (the minimum for alloy 2). It should be noted that in the material 5, the grain structure in the initial state is less uniform in comparison with other experimental alloys. In material 1, along with equiaxed grains, sections of sufficiently large elongated grains are observed. It can also be noted that the morphology of the ⁇ phase varies somewhat from alloy to alloy.
  • alloy 2 with a minimum amount of alloying elements the ⁇ -phase is predominantly localized in separate volumes between particles of the ⁇ -phase, then already starting from alloy 5, it has a certain connection and, in addition to the grain structure, has the form thin interlayers between grains of the ⁇ phase. With an increase in [Mo] eq of the material, these layers tend to thicken.
  • SUBSTITUTE SHEET (RULE 26) conglomerates from grains of a- and ⁇ -phases of a more complex shape.
  • Q is the number of diffusing alloying elements in the material during SPD, wt.%.
  • p is the number of alloying elements in the material
  • I Dttg I - the absolute value of the change in the content of the alloying element in the ⁇ - and a-phases, wt.% In the SPD process.
  • mccl is the content of the alloying element in the ⁇ phase before SPD
  • wt.% is the content of the alloying element in the ⁇ phase after SPD
  • Table 4 shows the calculated data on the number of diffusing alloying elements in the SPD process.
  • the obtained MRSA data were also used to estimate the volume fraction of phases in the material at the temperature
  • SUBSTITUTE SHEET (RULE 26) the most stable course of superplastic deformation at 775 ° C is observed both in the transverse and longitudinal directions with a minimum stress at the beginning of the flow, the absence of a pronounced “waviness” of the curve, and with monotonic hardening with an increase in the degree of deformation. This is due to the almost optimal ⁇ / ⁇ (1/1) phase ratio at the deformation temperature, as well as the maximum content of the most diffusively mobile ⁇ -stabilizers (nickel, iron) among the studied alloys, which should facilitate mass transfer processes upon realization of intergranular slippage (the total difference in the change in the content of alloying elements between the a and ⁇ phases in the SPD process is more than 1.9 wt.%).

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Powder Metallurgy (AREA)
  • Forging (AREA)
  • Conductive Materials (AREA)
  • Heat Treatment Of Steel (AREA)

Abstract

Le résultat technique obtenu lors de la mise en oeuvre de l'invention consiste à obtenir des feuilles en alliage de titane dans lesquelles la composition chimique est équilibrée de façon optimale avec la possibilité de produire sur la base des technologies standard existantes d'un produit final possédant des propriétés de déformation superplastique à basse température. Le résultat est obtenu en ce que le matériau en feuille pour déformation superplastique à basse température sur la base d'un alliage de titane, qui comprend en % en mass % 4,5-5,5Al, 4,5-5,5V, 0,1-1,0Мо, 0,8-l,5Fe, 0,l-0,5Cr, 0,l-0,5Ni, 0,16-0,250, le reste étant du titane et des impuretés, dans lequel la valeur de l'équivalent molibdénique [Мо]éq. > 5 et de l'équivalent structurel d'aluminium [Al]éq. < 8, les équivalents sont déterminés selon l'expression: [Mo]éq.=[Мо]+[V]/1,5+[Cr]1,25+[Fe]2,5+[Ni]/0,8 [Al]éq.=[Al]+[O]10+[Zr]/6.
PCT/RU2017/000266 2017-04-25 2017-04-25 Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température Ceased WO2018199791A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
RU2017139320A RU2691434C2 (ru) 2017-04-25 2017-04-25 Листовой материал на основе титанового сплава для низкотемпературной сверхпластической деформации
US16/607,592 US20200149133A1 (en) 2017-04-25 2017-04-25 Titanium alloy-based sheet material for low-temperature superplastic deformation
BR112019022330-4A BR112019022330B1 (pt) 2017-04-25 2017-04-25 Material de chapa para conformação superplástica a baixa temperatura
EP17907725.0A EP3617335B1 (fr) 2017-04-25 2017-04-25 Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température
CA3062762A CA3062762A1 (fr) 2017-04-25 2017-04-25 Materiau de tole a base d'alliage de titane pour la deformation superplastique a basse temperature
PCT/RU2017/000266 WO2018199791A1 (fr) 2017-04-25 2017-04-25 Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température
CN201780091937.6A CN111279003B (zh) 2017-04-25 2017-04-25 低温超塑性变形的钛合金系片材材料
JP2019558569A JP7028893B2 (ja) 2017-04-25 2017-04-25 低温超塑性変形のためのチタニウム合金ベースのシート材

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Application Number Priority Date Filing Date Title
PCT/RU2017/000266 WO2018199791A1 (fr) 2017-04-25 2017-04-25 Matériau en feuille à base d'alliage de titane pour déformation superplastique à basse température

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WO2018199791A1 true WO2018199791A1 (fr) 2018-11-01

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US (1) US20200149133A1 (fr)
EP (1) EP3617335B1 (fr)
JP (1) JP7028893B2 (fr)
CN (1) CN111279003B (fr)
BR (1) BR112019022330B1 (fr)
CA (1) CA3062762A1 (fr)
RU (1) RU2691434C2 (fr)
WO (1) WO2018199791A1 (fr)

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CN112680630B (zh) * 2020-12-04 2021-12-24 中国航发北京航空材料研究院 一种超高韧中强高塑tc32钛合金零件的真空热处理方法
CN115652142A (zh) * 2022-12-02 2023-01-31 昆明理工大学 一种新型钛合金及其制备方法

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See also references of EP3617335A4

Also Published As

Publication number Publication date
RU2017139320A (ru) 2019-05-13
EP3617335A1 (fr) 2020-03-04
CA3062762A1 (fr) 2019-11-28
JP7028893B2 (ja) 2022-03-02
BR112019022330A2 (pt) 2020-05-26
RU2017139320A3 (fr) 2019-05-13
EP3617335B1 (fr) 2021-11-17
CN111279003B (zh) 2022-01-28
RU2691434C2 (ru) 2019-06-13
JP2020517834A (ja) 2020-06-18
US20200149133A1 (en) 2020-05-14
CN111279003A (zh) 2020-06-12
EP3617335A4 (fr) 2020-08-19
BR112019022330B1 (pt) 2022-11-29

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