WO2024043804A1 - Matériau en feuille en alliage de titane et composant de système d'échappement - Google Patents
Matériau en feuille en alliage de titane et composant de système d'échappement Download PDFInfo
- Publication number
- WO2024043804A1 WO2024043804A1 PCT/RU2023/000248 RU2023000248W WO2024043804A1 WO 2024043804 A1 WO2024043804 A1 WO 2024043804A1 RU 2023000248 W RU2023000248 W RU 2023000248W WO 2024043804 A1 WO2024043804 A1 WO 2024043804A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sheet material
- alloy
- titanium
- phase
- titanium alloy
- Prior art date
Links
- 239000000463 material Substances 0.000 title claims abstract description 42
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims description 35
- 229910045601 alloy Inorganic materials 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910021341 titanium silicide Inorganic materials 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 abstract description 16
- 238000007254 oxidation reaction Methods 0.000 abstract description 16
- 229910052719 titanium Inorganic materials 0.000 abstract description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 9
- 230000002035 prolonged effect Effects 0.000 abstract 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 238000005272 metallurgy Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910021332 silicide Inorganic materials 0.000 description 6
- 230000007774 longterm Effects 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 238000000137 annealing Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000009856 non-ferrous metallurgy Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- -1 titanium hydrides Chemical class 0.000 description 1
- 238000010313 vacuum arc remelting Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
- F01N13/16—Selection of particular materials
Definitions
- the invention relates to non-ferrous metallurgy, in particular to the creation of sheet material from low-alloy titanium alloys that have heat resistance and oxidation resistance, as well as structural stability during long-term operating exposures in the temperature range up to 800°C and can be used for the manufacture of products that operate for a long time at high temperatures, in particular components of exhaust systems of vehicle engines.
- titanium-based alloys are used in the production of engine components such as intake and exhaust valves, housings, turbine impellers, pipes and tanks.
- engine components particularly exhaust systems, made from low-alloy titanium-based alloys are subject to operating temperatures in the order of 500-800°C. Therefore, the performance properties of materials, such as heat resistance and oxidation resistance, are a priority.
- the material used must have sufficient technological ductility, because the components are mainly produced by cold forming from rolled sheets and by bending welded pipes. To obtain high plasticity characteristics, it is important to create a structure in the material with a globular morphology of a-phase grains, since the globular microstructure has better molding properties than the needle structure.
- Creep which is the tendency of a solid material to slowly shift or permanently deform under stress, occurs when a metal is subjected to a constant tensile load at an elevated temperature. High creep resistance allows the material to be used for a long time without distortion of shape and size, while it is important to maintain the level of the original properties of the material.
- Known flat products and exhaust system components made from oxidation-resistant high-strength titanium alloy, which consists of, wt.%: from 0.06 to 0.5 iron, from 0.02 to 0.12 oxygen, from 0.15 to 0.46 silicon and the rest is titanium and random impurities.
- the titanium alloy has an average grain size of 15.9 microns or less.
- Rolled steel has high plastic properties, but has reduced resistance to high temperature oxidation.
- a known material for the exhaust system is made of a low-alloy titanium alloy, which has excellent resistance to high-temperature oxidation and corrosion and contains, wt.%, A1: 0.30-1.50%, Si: 0.10-1.0% and additionally containing Nb: 0.1-0.5 (US Patent No. 7166367, published 01/23/2007, IPC B32B15/01; C22C14/00, F01N7/16) - prototype.
- the material from this alloy has high strength and plastic properties at room and elevated temperatures, but has an insufficient level of resistance to high-temperature creep.
- the problem to be solved by the invention is the creation of sheet material with a globular microstructure from a low-alloy titanium alloy with the possibility of manufacturing a wide range of products from it, including those used in engine components and exhaust systems of vehicles.
- the technical result achieved by implementing the invention is the production of sheet material from a titanium alloy having a complex of high mechanical and operational properties, including an increased level of creep resistance, oxidation resistance, as well as structural stability during long-term operating exposures in the temperature range up to 800°C and with the possibility of cold forming.
- the titanium alloy contains components in the following ratios, wt.%:
- the ratio of Mo, mass. %, to Si, wt. %, is 0.4 - 3.
- the sheet material contains at least 90 vol.% a-phase in the structure.
- the total content of the 0-phase and intermetallic particles of titanium silicides is 0.5 -5 vol. %.
- the average grain size of the a-phase ranges from 5 to 100 ⁇ m.
- the sheet material is made in the form of rolled sheets up to 6 mm thick. Also, the technical result is achieved by the fact that a component of the vehicle exhaust system is proposed that operates for a long time at high temperatures and is made of titanium alloy sheet material.
- the titanium alloy material contains alloying elements from various groups of stabilizers: alpha stabilizers: aluminum, oxygen, carbon, nitrogen; beta stabilizers: molybdenum, silicon.
- Aluminum improves heat resistance and creep resistance, reducing scale formation at high temperatures. temperature.
- the aluminum content in the alloy is taken to be from 1.5-3.0 wt.%.
- the maximum aluminum content in the alloy is limited to 3.0 wt.%.
- Alloying of the alloy with molybdenum in an amount of 0.1 -0.5 wt.%. helps increase strength due to solid solution strengthening and the appearance of p-phase interlayers in the structure, which are interphase boundaries and inhibit the movement of dislocations during deformation, and also prevent the collective growth of a-grains at high temperatures during heat treatment and operation.
- Molybdenum content is more than 0.5 wt.%. reduces heat resistance, since the temperature of the polymorphic transformation of the alloy decreases and the proportion of the P-phase in the structure increases.
- the silicon content in the alloy is set in the range from 0.1 to 0.6 wt. %. In this range, silicon forms an intermetallic compound with titanium - a silicide of complex stoichiometric composition (Ti x Si y ).
- the formation of the required amount of silicides in the alloy increases heat resistance, creep resistance and prevents grain growth at high temperatures.
- silicon significantly increases the oxidation resistance of the alloy up to a concentration of 0.8 wt%. At higher concentrations, technological plasticity/formability decreases due to the formation of coarse-grained silicides.
- the maximum hydrogen content in the alloy limited to 0.015 wt.%, avoids embrittlement of the alloy due to the possible formation of titanium hydrides.
- the iron content in the alloy is limited to 0.2 wt. %, because higher content has a negative effect on creep resistance and short-term heat resistance.
- the main factor in the stability of the structure during long-term operating exposures at elevated temperatures is the presence of particles that inhibit grain growth. They are both particles (3-phases in the alloy and particles of silicides. The presence of both types of particles in the alloy is very important, which is achieved by close contents of Mo and Si.
- the preferred ratio (3-isomorphic molybdenum and 0-eutectoid silicon Mo/ Si in weight percent is in the range from 0.4 to 3. This ratio allows for increased oxidation resistance, increased creep resistance and structural stability during long service exposures
- composition of elements introduced into the alloy in the claimed ratio and individually characterized by a favorable effect on the oxidation resistance of titanium makes it possible to achieve an additive effect in terms of obtaining high values creep resistance of the alloy while providing strength and plastic properties in combination with oxidation resistance in relation to known low-alloy titanium alloys.
- the globular structure of a-phase grains has higher values of plasticity and formability than the acicular structure. For this reason, to improve the formability of sheet material, a homogeneous globular microstructure with an average a-phase grain size of 5 to 100 ⁇ m is preferred. Obtaining a microstructure with an average a-phase grain size of less than 5 ⁇ m requires a large number of technological operations and, accordingly, high costs; in a microstructure with an average a-phase grain size of more than 100 ⁇ m, the boundaries of large grains become the starting points of destruction during fracture.
- Measurement of the average diameter of a-phase grains in the structure of a titanium workpiece is carried out in accordance with the methodology of the international standard ASTM E112.
- the fraction of O-phase particles and silicides is measured using a scanning electron probe microscope (SEM) in backscattered electron mode and processing the resulting images using software for quantitative analysis of the microstructure by elemental contrast.
- SEM scanning electron probe microscope
- the preferred content of the a-phase in the material is at least 95 vol.%.
- the total content of the 0-phase and intermetallic particles of titanium silicides in the material in the range of 0.5-5 vol.% helps to increase the resistance to high-temperature creep.
- the industrial applicability of the invention is confirmed by an example of its specific implementation.
- the ingot was subjected to deformation by forging and subsequent rolling to obtain a roll with a thickness of 0.9 mm; the final stages of rolling were performed below the polymorphic transformation temperature of 945 °C, which is necessary for the formation of the globular structure of a-grains.
- samples were cut out in the as-delivered state.
- tensile tests were carried out at temperatures of 20°C, 500°C, 700°C; to evaluate the material's stampability criterion, deep drawing tests according to Eriksen were carried out.
- the values of the tensile mechanical properties of the material in the delivered state (annealed state) are given in Table 2 and the comparative graph presented in Fig. 1. Table 2
- the average grain size of the a-phase in the longitudinal section determined in accordance with the international standard ASTM E112, is 15 ⁇ m.
- the proportion of the a-phase was 98 vol.%, and the proportion of the 0-phase and titanium silicide particles was 2 vol.%.
- the fraction of 0-phase and titanium silicide particles was measured using a scanning electron probe microscope (SEM) in backscattered electron mode and calculating the fraction of phases in an image analysis program.
- the grain structure of the material with particles of titanium silicides and interlayers of the 0-phase after annealing at 625°C for 1000 hours does not change in comparison with the initial one (Fig. 6), which indicates the stability of the structure.
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Powder Metallurgy (AREA)
Abstract
L'invention se rapporte à la métallurgie, notamment à un matériau en feuille en alliages de titane, possédant une résistance à la chaleur et une résistance à l'oxydation, ainsi qu'une stabilité structurelle lors de longues durées d'exposition pendant l'exploitation dans une plage de températures allant jusqu'à 800°C, et peut être utilisée pour fabriquer des composants de systèmes d'échappement de moyens de transport. Ce matériau en feuille en alliage de titane pour produire des composants comprend, en % en poids: aluminium: 1,5-3,0; molybdène: 0,1-0,5; silicium: 0,1-0,6; fer: pas plus de 0,2; oxygène: pas plus de 0,15; carbone: pas plus de 0,1; azote: pas plus de 0,03; hydrogène: pas plus de 0,015; le reste se composant de titane. Ce matériau en feuille possède des valeurs élevées de résistance au fluage, de résistance à l'oxydation, et possède également une structure stable lors de longues durées d'exposition pendant l'exploitation dans une plage de températures allant jusqu'à 800°C; ce matériau se prête à la mise en forme à froid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2022122702A RU2785110C1 (ru) | 2022-08-22 | Листовой материал из титанового сплава и компонент выхлопной системы | |
| RU2022122702 | 2022-08-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2024043804A1 true WO2024043804A1 (fr) | 2024-02-29 |
Family
ID=90013684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/RU2023/000248 WO2024043804A1 (fr) | 2022-08-22 | 2023-08-14 | Matériau en feuille en alliage de titane et composant de système d'échappement |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2024043804A1 (fr) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166367B2 (en) * | 2004-03-12 | 2007-01-23 | Kobe Steel, Ltd. | Titanium alloy having excellent high-temperature oxidation and corrosion resistance |
| RU2681089C2 (ru) * | 2017-05-12 | 2019-03-04 | Хермит Эдванст Технолоджиз ГмбХ | Заготовка из сплава на основе титана для упругих элементов с энергоемкой структурой |
| WO2020075667A1 (fr) * | 2018-10-09 | 2020-04-16 | 日本製鉄株式会社 | FIL D'ALLIAGE DE TITANE DE TYPE α+β ET PROCÉDÉ DE PRODUCTION DE FIL D'ALLIAGE DE TITANE DE TYPE α+β |
| RU2776521C1 (ru) * | 2021-07-29 | 2022-07-21 | Публичное Акционерное Общество "Корпорация Всмпо-Ависма" | Сплав на основе титана и изделие, выполненное из него |
-
2023
- 2023-08-14 WO PCT/RU2023/000248 patent/WO2024043804A1/fr active Search and Examination
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7166367B2 (en) * | 2004-03-12 | 2007-01-23 | Kobe Steel, Ltd. | Titanium alloy having excellent high-temperature oxidation and corrosion resistance |
| RU2681089C2 (ru) * | 2017-05-12 | 2019-03-04 | Хермит Эдванст Технолоджиз ГмбХ | Заготовка из сплава на основе титана для упругих элементов с энергоемкой структурой |
| WO2020075667A1 (fr) * | 2018-10-09 | 2020-04-16 | 日本製鉄株式会社 | FIL D'ALLIAGE DE TITANE DE TYPE α+β ET PROCÉDÉ DE PRODUCTION DE FIL D'ALLIAGE DE TITANE DE TYPE α+β |
| RU2776521C1 (ru) * | 2021-07-29 | 2022-07-21 | Публичное Акционерное Общество "Корпорация Всмпо-Ависма" | Сплав на основе титана и изделие, выполненное из него |
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