EP4261300A1 - Ternäre titanlegierung, verfahren zu ihrer herstellung und verwendung - Google Patents

Ternäre titanlegierung, verfahren zu ihrer herstellung und verwendung Download PDF

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Publication number
EP4261300A1
EP4261300A1 EP22214082.4A EP22214082A EP4261300A1 EP 4261300 A1 EP4261300 A1 EP 4261300A1 EP 22214082 A EP22214082 A EP 22214082A EP 4261300 A1 EP4261300 A1 EP 4261300A1
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Prior art keywords
alloy
temperature
cooling
annealing
rhenium
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EP22214082.4A
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English (en)
French (fr)
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EP4261300B1 (de
EP4261300C0 (de
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Piotr KWASNIAK
Marek MUZYK
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KGHM Polska Miedz SA
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KGHM Polska Miedz SA
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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
    • 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
    • C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • 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 a ternary alloy of titanium, silicon, and rhenium, and a method for producing a ternary alloy of titanium, silicon, and rhenium, which allows for providing high strength or plasticity, and to its applications.
  • phase structure a phase -a uniform part of a metal or an alloy with a specific and periodic atomic structure
  • shape the mechanical and physicochemical properties of a material; they include [1-3]:
  • Ti alloys include pseudo-alpha alloys, which are basically two-phase alloys, but the share of the alpha phase is predominant - the remaining elements of the structure usually account for several percent by volume [1-3].
  • Pseudo-alpha alloys have been designed to work at high temperatures, and they are characterised by a complex chemical composition, e.g.
  • Ti-6-2-4-2-S alloy with the following composition: Ti-6Al-2Sn-4Zr-2Mo-0.1Si, TIMETAL 1100: Ti-6Al-2.7Sn-4Zr-0.4Mo-0.4Si, TIMTETAL 685: Ti-6Al-5Zr-0.5Mo-0.25Si, TIMETAL 834 Ti-5.8Al-4Sn-3.5Zr-0.5Mo-0.7Nb-0.35Si-0.06C [2,5]. Alloying elements with the highest share are Al, Sn, and Zr, serving the function of stabilisers of the alpha phase, while the remaining elements are responsible for the precipitation of additional phases - the beta phase and intermetallic precipitates.
  • pseudo-alpha alloys are their very complex chemical composition, hindering their further improvement, and low ductility, usually not exceeding 12% of the breaking strain, due to which these alloys cannot be freely shaped at low temperatures.
  • the document FR2213986B1 presents a titanium alloy with the following additives: 0.05-0.1% Re, 6-7.5% Al, 0.2-2% Zr, 0.5-2% Sn, 1.5-2.7% Mo, 0.2-1.2% W, 0.1-0.35% Si, and 0.2-0.5% Cr.
  • This alloy is characterised by high strength and thermal stability at a temperature of 500°C, a high fatigue limit and resistance to creep. If is found useful, e.g. in the blades of gas and steam turbines.
  • This alloy has a very complex chemical composition - it contains numerous alloying additives.
  • the document EP2687615B1 describes a titanium alloy with good resistance to oxidation, characterised by high strength at elevated temperatures.
  • the alloy can contain between 4.5 and 7.5% of Al, between 2 and 8% of TiN, between 1.5 and 6.5% of Nb, between 0.1 and 2.5% of Mo, between 0.1 and 0.6% of Si, up to 0.2% of O, and up to 0.10% of C.
  • This alloy does not contain rhenium; moreover, the alloy contains numerous alloying additives.
  • the document US10183331B2 discloses a method for producing a titanium alloy using the SPS method, meaning spark plasma sintering from titanium powders.
  • the alloy contains 42% to 49% of aluminium, between 0.05% and 1.5% of boron, at least 0.2% of at least one element selected from a group consisting of tungsten, rhenium, and zirconium, possibly 0% to 5% of at least one element selected from a group consisting of chromium, niobium, molybdenum, silicon, and carbon, with the remaining part being titanium.
  • the document CN106119603A presents an alloy resistant to corrosion, containing the following elements: 6-7 parts by weight of copper, 6-7 parts by weight of tantalum, 5-6 parts by weight of chromium, 6-7 parts by weight of tungsten, 1.5-2 parts by mass of rhenium, 0-1.5 parts by weight of silicon, 7-8 parts by mass of cobalt, and 26-38 parts by mass of titanium.
  • the ternary titanium alloy according to the invention contains titanium, between 0.4 and 0.6% by weight of silicon, between 0.2 and 1% by weight of rhenium, and possible impurities in the form of oxygen, nitrogen, carbon, and iron, preferably in a total amount below 1.05 wt%.
  • the silicon content is 0.45 wt%.
  • the rhenium content is between 0.5 and 1 wt%, preferably 1 wt%.
  • the method for producing a ternary titanium alloy according to the invention comprises the following steps:
  • the recasting temperature is higher than the melting point of Re and lower than the boiling point of Ti.
  • Recasting of the mixture in step (ii) can be performed using the arc melting method.
  • recasting of the mixture in step (ii) is performed five times.
  • homogenisation annealing in step (iv) is performed at a temperature of at least 882°C, preferably at least 900°C.
  • homogenisation annealing in step (iv) is performed for a time of at least 30 minutes.
  • cooling in step (v) is performed in water, preferably at room temperature.
  • step (vi) forming processes can be performed by cold rolling of the cooled alloy.
  • cold rolling in step (vi) is performed until reaching a reduction of at least 50% of the thickness of the material, preferably 50-80% of the thickness of the material.
  • recrystallisation annealing in step (vii) is performed at a temperature between 810 and 830°C, preferably 820°C, and cooling is performed in accordance with step (viii) with a furnace, preferably at a rate of at least 1°C/min, or in the air, preferably at room temperature.
  • recrystallisation annealing in step (vii) is performed at a temperature higher than 882°C, preferably approximately 950°C, and cooling is performed in accordance with step (viii) in water.
  • recrystallisation annealing in step (vii) is performed for a time of at least 10 minutes, preferably for a time of 10 minutes.
  • step (vi) forming processes can be performed by hot forging above the ⁇ -> ⁇ transition temperature.
  • the ternary alloys according to the invention are applicable to the production of bearing elements of lightweight constructions and/or critical elements operating at high temperatures, preferably valves, connecting rods, shafts and/or structural elements, preferably bodies, exhaust gas discharge collectors and/or engine sheathing elements and/or drives and/or blades and/or controls of gas turbines.
  • the ⁇ transition temperature of the alloy is 882°C
  • the melting point of rhenium is 3185°C
  • the boiling point of titanium is approximately 3287°C.
  • Fig. 1 presents the microstructure of a Ti-Si-1Re alloy in a state of equilibrium, i.e. after slow cooling from 820°C (treatment A) with visible intercrystalline precipitates - type I, and located inside the grains - type II (transmission electron microscopy);
  • Fig. 2 presents the microstructure of a Ti-Si-Re alloy after fast cooling from 950°C (treatment B) with indicated martensite plates and precipitates of Ti-Si phases (transmission electron microscopy and electron diffraction);
  • Fig. 1 presents the microstructure of a Ti-Si-1Re alloy in a state of equilibrium, i.e. after slow cooling from 820°C (treatment A) with visible intercrystalline precipitates - type I, and located inside the grains - type II (transmission electron microscopy);
  • Fig. 2 presents the microstructure of a Ti-Si-Re alloy after fast cooling from 950°C (treatment B) with indicated martensite plates and precipitates of Ti-Si phases (transmission electron
  • Fig. 3 presents the mechanical properties of pure titanium, Ti-Re and Ti-Si alloys (the commercial Timetal XT alloy indicated as TiXT), and Ti-Si-Re alloys, materials in a normalised condition after type A heat treatment, i.e. slow cooling from 820°C (the static tension test)
  • Fig. 4 presents the structure (a) and mechanical properties (b) of pure titanium, Ti-Re and Ti-Si alloys (the commercial Timetal XT alloy indicated as TiXT), and Ti-Si-Re alloys - materials in a metastable condition after supersaturation from a temperature of 950°C, i.e. after treatment B (EBSD images of the microstructures of selected systems, and the static tension test).
  • Ternary Ti-Si-Re alloys were prepared using the commercial Timetal XT alloy, containing 0.45 wt% of silicon. This material was recast with a rhenium additive, using the following procedure:
  • Homogenisation annealing was performed at a temperature above the ⁇ -> ⁇ transition temperature of the alloy, i.e. above 882°C. In an embodiment, annealing was performed at a temperature of 900°C and over a time of 30 minutes. This step was supposed to homogenise the microstructure (elimination of unpreferable morphology comprising zones of frozen grains, columnar grains, and dendrites of variable size) and chemical composition.
  • Treatment A Recrystallisation annealing at a temperature of 820°C, minimum time of 10 minutes, cooling in the air or with a furnace. This step of the treatment was performed at a temperature close to the end of stability of the ⁇ -Ti phase, resulting in full recrystallisation of the material and obtaining a homogeneous, equiaxial microstructure (the reference condition for commercial materials).
  • Treatment B Recrystallisation annealing at a temperature of 950°C, minimum time of 10 minutes, cooling in water. This version of treatment was performed at the temperature of stability of the ⁇ phase. Fast cooling in water resulted in a metastable ⁇ -Ti structure, supersaturated with rhenium, with a minimal amount of precipitates.
  • binary Ti-Re alloys were also prepared.
  • the input materials Ti with purity of 99.98 wt% and Re with purity of 99.9 wt% (according to the received technical specification) were cut and cleaned chemically and ultrasonically.
  • Four compositions/mixtures of substrates were prepared, with the following Re concentrations: 0 (pure Ti), 0.2 wt%, 0.5 wt%, and 1 wt%, which constituted an input for the production of solid materials.
  • the binary alloys were prepared using the same method as for the ternary alloys, but using only treatment A in step (vii).
  • Heat treatment A resulted in achieving a homogeneous, equiaxial structure of the material, consisting of a hexagonal phase saturated with rhenium and silicon, and two types of precipitates of a submicrometric size, present inside the grains and on their boundaries, as presented in Figure 1 .
  • Heat treatment B resulted in shaping a dispersed martensitic structure (a supersaturated hexagonal solution of Ti), with thickness of martensite plates in the order of 200 nm, with larger alpha grains and TiSi precipitates - Figs. 2 and 4 .
  • the different morphology of the Ti-Si-Re alloy achieved by means of two heat treatments resulted in significantly different properties of the material, which are presented in Figures 3 and 4 .
  • Type A treatment allowed for achieving high strength and very high plasticity - the yield point higher by approximately 100 MPa, and the breaking strain higher by 11% compared to the commercial Timetal XT alloy with a composition of Ti-0.5Si (0.5 wt% ofSi).
  • the increase in the yield point and the breaking strain was 20% and 40%, respectively.
  • the yield point increased by 225%, and the Ti-Si-Re alloy retained over 80% of plasticity of pure Ti, which was unheard- of in the previous solutions.
  • the use of the B-type treatment increased the strength of the Ti-Si-Re alloy to a level of 950 MPa - the tensile strength, decreasing the plasticity of the alloy to a level of 17% of the breaking strain.
  • increases in strength of 40% and 147% were achieved for the Timetal XT alloy (Ti-05Si) and pure titanium, respectively.

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Silicon Compounds (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Powder Metallurgy (AREA)
EP22214082.4A 2022-04-11 2022-12-16 Ternäre titanlegierung, verfahren zu ihrer herstellung und verwendung Active EP4261300B1 (de)

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PL440911A PL440911A1 (pl) 2022-04-11 2022-04-11 Trójskładnikowy stop tytanu, sposób jego wytwarzania i zastosowanie

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2213986A1 (en) * 1973-01-16 1974-08-09 Glazunov Sergei Titanium alloy for gas and steam turbine blades - contg. rhenium, aluminium, zirconium, tin, molybdenum, tungsten, silicon and chromium
JPH08246192A (ja) * 1995-03-03 1996-09-24 Kobe Steel Ltd 光触媒活性を有する酸化処理チタン又はチタン基合金材及びその製法
US20040094241A1 (en) * 2002-06-21 2004-05-20 Yoji Kosaka Titanium alloy and automotive exhaust systems thereof
EP2687615A2 (de) * 2012-07-19 2014-01-22 RTI International Metals, Inc. Titanlegierung mit hoher Oxidationsbeständigkeit und hoher Festigkeit bei hohen Temperaturen
CN106119603A (zh) 2016-08-15 2016-11-16 谢光玉 一种耐腐蚀合金材料
US10183331B2 (en) 2013-06-11 2019-01-22 Centre National de la Recherche Scientifique—CNRS— Method for manufacturing a titanium-aluminum alloy part

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2213986A1 (en) * 1973-01-16 1974-08-09 Glazunov Sergei Titanium alloy for gas and steam turbine blades - contg. rhenium, aluminium, zirconium, tin, molybdenum, tungsten, silicon and chromium
FR2213986B1 (de) 1973-01-16 1976-05-14 Glazunov Sergei
JPH08246192A (ja) * 1995-03-03 1996-09-24 Kobe Steel Ltd 光触媒活性を有する酸化処理チタン又はチタン基合金材及びその製法
US20040094241A1 (en) * 2002-06-21 2004-05-20 Yoji Kosaka Titanium alloy and automotive exhaust systems thereof
EP2687615A2 (de) * 2012-07-19 2014-01-22 RTI International Metals, Inc. Titanlegierung mit hoher Oxidationsbeständigkeit und hoher Festigkeit bei hohen Temperaturen
EP2687615B1 (de) 2012-07-19 2017-05-10 RTI International Metals, Inc. Titanlegierung mit hoher Oxidationsbeständigkeit und hoher Festigkeit bei hohen Temperaturen
US10183331B2 (en) 2013-06-11 2019-01-22 Centre National de la Recherche Scientifique—CNRS— Method for manufacturing a titanium-aluminum alloy part
CN106119603A (zh) 2016-08-15 2016-11-16 谢光玉 一种耐腐蚀合金材料

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
C. LEYENSM. PETERS: "Titanium and Titanium Alloys. Fundamentals and Applications", 2003, WILEY-VCH VERLAG GMBH & CO. KGAA
D. BANERJEEJ.C. WILLIAMS: "Perspectives on Titanium Science and Technology", ACTA MATERIALIA, vol. 61, 2013, pages 844
G. LUTHERINGJ.C. WILLIAMS: "Titanium", 2007, SPRINGER
R. BOYERG. WELSCHE.W. COLLINGS: "Materials Properties Handbook : Titanium Alloys", 1994, ASM INTERNATIONAL
STOPY TIMETAL 685, TIMETAL 834, TIMETAL 1100, Retrieved from the Internet <URL:https://www.timet.com/literature/datasheets.html>

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EP4261300B1 (de) 2024-07-24
EP4261300C0 (de) 2024-07-24
PL440911A1 (pl) 2023-10-16

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