EP4411010A1 - Titanium-based alloy and article manufactured from same - Google Patents
Titanium-based alloy and article manufactured from same Download PDFInfo
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- EP4411010A1 EP4411010A1 EP22873266.5A EP22873266A EP4411010A1 EP 4411010 A1 EP4411010 A1 EP 4411010A1 EP 22873266 A EP22873266 A EP 22873266A EP 4411010 A1 EP4411010 A1 EP 4411010A1
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- alloy
- titanium
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- silicon
- oxygen
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- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 43
- 239000000956 alloy Substances 0.000 title claims abstract description 43
- 239000010936 titanium Substances 0.000 title claims description 8
- 229910052719 titanium Inorganic materials 0.000 title claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001069 Ti alloy Inorganic materials 0.000 claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000010703 silicon Substances 0.000 claims abstract description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 8
- 239000011733 molybdenum Substances 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000007774 longterm Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000009856 non-ferrous metallurgy Methods 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910009601 Ti2Cu Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021341 titanium silicide Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- -1 titanium hydrides Chemical class 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000010313 vacuum arc remelting Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Exhaust Silencers (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Physical Vapour Deposition (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
The invention relates to nonferrous metallurgy, namely to the development of low-alloyed titanium alloys characterized by high-temperature strength and thermal stability, and can be used for manufacture of articles intended for long-term operation at high temperatures, namely components of exhaust systems of vehicle engines. Titanium alloy containing aluminum, molybdenum, silicon, oxygen, nitrogen, iron, hydrogen, with the alloy components taken in the following ratio, % wt.:Aluminium1.5 to 3.0Molybdenum0.1 to 0.5Silicon0.1 to 0.6Iron0.2 maxOxygen0.15 maxCarbon0.1 maxNitrogen0.03 maxHydrogen0.015 maxTitanium and inevitable impurities - balance,which in one embodiment additionally contains copper 0.5 to 1.5% wt., and article made thereof.A technical result of the embodiment of invention is the production of titanium alloy characterized by a combination of high mechanical and performance properties, including a higher level of creep resistance, with capability of cold forming.
Description
- The invention relates to nonferrous metallurgy, namely to the development of low-alloyed titanium alloys characterized by high-temperature strength and thermal stability, and can be used for manufacture of articles intended for long-term operation at high temperatures, namely components of exhaust systems of vehicle engines.
- In various commercial applications, such as internal combustion engines and exhaust systems, titanium alloys are used for manufacture of their components such as intake and exhaust valves, housings, turbine impellers, pipes and tanks. In many of these applications, engine components, particularly exhaust systems, made of low-alloyed titanium alloys are subject to operating temperatures of 500 to 800 °C. Therefore, the performance properties of alloys, such as high-temperature strength and oxidation resistance, are a priority. In addition, the material used shall exhibit sufficient process ductility because the components are mainly manufactured by cold forming of rolled sheet metal and by bending of welded tubes.
- As designers of internal combustion engines improve the efficiency of engines, the characteristics such as boost pressure, compression ratio and operating temperatures improve accordingly. Increasing the level of these characteristics results in the need for materials that will resist (creep) strain at higher operating temperatures and pressures in the combustion chamber and exhaust system than are currently achievable with conventional low-alloyed titanium alloys. Creep, which is the susceptibility of a solid material to slow offset or residual strain under load, occurs when metal is subjected to a constant tensile stress at 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 original material properties.
- Consequently, materials which, in addition to their low price, have the best combination of high mechanical and performance properties are in demand.
- There is a known oxidation-resistant high-strength titanium alloy consisting mainly of (% wt.): 0.2 to less than 0.5 iron, 0.02 to less than 0.12 oxygen, 0.15 to 0.6 silicon, and balance - titanium and inevitable impurities. The alloy additionally contains at least one element selected from the group consisting of Al, Nb, V, Mo, Sn, Zr, Ni, Cr and Ta, with a total content of less than 1.5 (
US Patent No. 7767040 ,published 03.08.2010 , IPC C22C14/00). - The alloy exhibits high plastic properties, but has low resistance to high-temperature oxidation.
- There is a known low-alloyed titanium alloy characterized by excellent resistance to high-temperature oxidation and corrosion, which is used as a material for exhaust system of vehicles or motorbikes, containing (% wt.) Al: 0.30 to 1.50%, Si: 0.10 to 1.0%, and additionally containing Nb: 0.1 to 0.5 (
US Patent No. 7166367, published 23.01.2007 , IPC B32B15/01; C22C14/00, F01N7/16) - prototype. - The alloy exhibits high strength and plastic properties at room and elevated temperature, but has insufficient level of high-temperature creep resistance.
- The objective of this invention is to develop low-alloyed titanium alloy enabling the manufacture of a wide range of articles thereof, including those used in engine components and exhaust systems of vehicles.
- A technical result of the embodiment of invention is the production of titanium alloy characterized by a combination of high mechanical and performance properties, including a higher level of creep resistance, with capability of cold forming.
- A technical result is achieved by means of titanium alloy containing aluminum, molybdenum, silicon, oxygen, nitrogen, iron, hydrogen, with the alloy components taken in the following ratio, % wt.:
Aluminum 1.5 to 3.0 Molybdenum 0.1 to 0.5 Silicon 0.1 to 0.6 Iron 0.2 max Oxygen 0.15 max Carbon 0.1 max Nitrogen 0.03 max Hydrogen 0.015 max - Titanium and inevitable impurities - balance,
which in one embodiment additionally contains copper 0.5 to 1.5% wt., and article made thereof. - The alloying elements are introduced into the alloy composition from various groups of stabilizers: alpha-stabilizers: aluminum, oxygen, carbon, nitrogen; beta-stabilizers: molybdenum, iron, silicon. In one embodiment of the invention, a beta-stabilizer - copper is introduced into the alloy.
- Aluminum increases high-temperature strength and creep resistance, reducing the scale formation at high temperature. Aluminum content in the alloy is set to contain 1.5 to 3.0% wt. To maintain optimum process ductility, the maximum aluminum content in the alloy is limited to 3.0% wt.
- The content of oxygen, nitrogen and carbon within the specified limits, in addition to strength improvement, increases the temperature of allotropic transformation of titanium and ensures the maintenance of a high level of strength and ductility. Higher concentrations of oxygen, carbon and nitrogen decrease process ductility and impact strength of the alloy.
- A group of beta-stabilizers (Mo, Fe, Si, Cu).
- Molybdenum alloying of the alloy in the amount of 0.1 to 0.5% wt. promotes strength improvement due to the occurrence of β-phase layers in the structure, which act as interphase boundaries and inhibit the dislocation motion during deformation, as well as prevent the collective growth of α-grains at high temperatures. Molybdenum content exceeding 0.5% wt. reduces high-temperature strength, since beta transus temperature of the alloy decreases and the amount of β-phase in the structure increases.
- The presence of silicon in the alloy, which is present in the titanium solid solution, increases the creep resistance. Silicon content in the alloy is set to contain 0.1 to 0.6% wt. Within this range, silicon forms intermetallic compound with titanium - silicide (Ti3Si). The formation of the required amount of silicides in the alloy increases high-temperature strength, creep resistance, and prevents the growth of α-grains at high temperatures. In addition, silicon significantly increases the oxidation resistance of the alloy up to a concentration of 0.6% wt. At higher concentrations, the process ductility/formability decreases.
- The alloy can be additionally alloyed with copper. Copper, being a eutectoid-forming element and having high solubility in titanium alpha phase, provides the effect of solid-solution strengthening. The formation of Ti2Cu intermetallic particles, limiting the migration of boundaries at high temperature, helps to increase the high-temperature strength of the alloy, however, the excessive number of Ti2Cu phase particles reduces the alloy ductility at room temperature, therefore the copper content in the proposed alloy is determined to be 1.5% wt. maximum.
- The maximum hydrogen content in the alloy, limited to 0.015% wt., helps to avoid embrittlement of the alloy due to potential formation of titanium hydrides.
- The composition of elements introduced into the alloy in the specified ratio and individually characterized by a favorable effect on the oxidation resistance of titanium, helps to achieve an additive effect in terms of obtaining high creep resistance values of the alloy while ensuring strength and plastic properties in combination with satisfactory oxidation resistance compared to known low-alloyed titanium alloys.
- Industrial applicability of the invention is proved by the exemplary embodiment.
- Two compositions of ingots weighing 2100 kg were melted according to the industrial process using vacuum arc remelting method to test the properties of the proposed alloy. Chemical composition No. 1 and chemical composition No. 2 of the alloy are given in Table 1.
Table 1 Alloy compo sition Sampling area Content of elements, % wt. Ti Al Mo Si Cu Fe O C N H No. 1 Ingot top base 1,92 0,25 0,41 - 0,034 0,098 0,003 <0,003 <0,003 Ingot bottom base 1,91 0,25 0,39 - 0,033 0,095 0,003 <0,003 <0,003 No. 2 Ingot top base 2,37 0,23 0,31 0,9 0,038 0,121 0,003 <0,003 <0,003 Ingot bottom base 2,39 0,22 0,22 0,79 0,033 0,120 0,003 <0,003 <0,003 - Ingots were hot worked by forging and subsequent rolling to produce coils with a thickness of 0.9 mm. Samples in delivery condition were taken to evaluate the mechanical properties of the alloys. Tensile tests at temperatures of 20 °C, 500 °C, 700 °C were performed to analyze the mechanical properties; Erichsen deep drawing cup tests were performed to evaluate the material formability criterion. The values of tensile properties of the alloy in delivery condition (as-annealed) are given in Table 2 and comparative graph shown in
Fig. 1 .Table 2 Alloy composi tion Test temperature,°C Sampling direction Mechanical properties Erichsen test criterion, Average indentation depth, IE, mm Proof stress σ0.2, MPa Tensile strength σB, MPa Elongation δ, % No. 1 20 °C Longitudinal 500 621 21 5,7 Transverse 542 597 21,5 500 °C Longitudinal 212 332 21 Transverse 209 316 21,6 700 °C Longitudinal 91 119 >30 Transverse 102 117 >30 No. 2 23 °C Longitudinal 496 614 22,4 5,8 Transverse 540 588 23,9 500 °C Longitudinal 240 399 18,4 Transverse 253 352 28 700 °C Longitudinal 99 109 >30 Transverse 103 113 >30 - In order to simulate the material performance during operation in the article, isothermal annealing of samples of both compositions was performed in static laboratory air at temperatures of 560 °C and 800 °C with a holding time of 100 and 200 hours respectively. After that, the oxidation resistance was evaluated by calculating the increase in weight of the samples expressed in mg/cm2. The results of evaluations of oxidation resistance in comparison with the prototype alloy are shown in the graphs of alloy weight increase versus the square root of oxidation time at 560 °C and 800 °C shown in
Fig. 2 andFig. 3 respectively. - In addition, creep resistance expressed as a function of relative strain at a stress of 30 MPa was determined on samples of alloy in the delivery condition at 500 °C for 100 hours. The results of creep resistance of the claimed alloy in comparison with the prototype alloy are shown in the graph given in
Fig. 4 . - Analysis of test results and evaluation data showed that the proposed alloy exhibits a combination of high mechanical and performance properties, including high-temperature creep resistance compared to known low-alloyed alloys. The results of evaluation of oxidation resistance of alloy samples after long-term isothermal annealing demonstrate the durability of the material.
Claims (3)
- Titanium alloy containing aluminum, molybdenum, silicon, iron, oxygen, carbon, nitrogen, hydrogen, characterized in that the alloy components are taken in the following ratio, % wt.:
Aluminum 1.5 to 3.0 Molybdenum 0.1 to 0.5 Silicon 0.1 to 0.6 Iron 0.2 max Oxygen 0.15 max Carbon 0.1 max Nitrogen 0.03 max Hydrogen 0.015 max - The alloy according to claim 1, characterized in that it additionally contains copper 0.5-1.5% wt.
- Titanium alloy article, characterized in that it is made of the alloy under claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2021128341A RU2781823C1 (en) | 2021-09-27 | Titanium-based alloy and component of the exhaust system | |
| PCT/RU2022/000285 WO2023048593A1 (en) | 2021-09-27 | 2022-09-19 | Titanium-based alloy and article manufactured from same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4411010A1 true EP4411010A1 (en) | 2024-08-07 |
Family
ID=85719573
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP22873266.5A Pending EP4411010A1 (en) | 2021-09-27 | 2022-09-19 | Titanium-based alloy and article manufactured from same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20240247341A1 (en) |
| EP (1) | EP4411010A1 (en) |
| KR (1) | KR20240070638A (en) |
| CN (1) | CN117999374A (en) |
| WO (1) | WO2023048593A1 (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040094241A1 (en) | 2002-06-21 | 2004-05-20 | Yoji Kosaka | Titanium alloy and automotive exhaust systems thereof |
| EP1574589B1 (en) | 2004-03-12 | 2012-12-12 | Kabushiki Kaisha Kobe Seiko Sho | Titanium alloy having excellent high-temperature oxidation and corrosion resistance |
| RU2681089C2 (en) * | 2017-05-12 | 2019-03-04 | Хермит Эдванст Технолоджиз ГмбХ | Titanium-based alloy billet for elastic elements with energy-intensive structure |
| JP6933255B2 (en) * | 2017-08-03 | 2021-09-08 | 日本製鉄株式会社 | Titanium ingots and their manufacturing methods, as well as titanium slabs |
| JP6965986B2 (en) * | 2018-10-09 | 2021-11-10 | 日本製鉄株式会社 | Manufacturing method of α + β type titanium alloy wire and α + β type titanium alloy wire |
-
2022
- 2022-09-19 KR KR1020247013991A patent/KR20240070638A/en unknown
- 2022-09-19 US US18/693,978 patent/US20240247341A1/en active Pending
- 2022-09-19 CN CN202280064840.7A patent/CN117999374A/en active Pending
- 2022-09-19 WO PCT/RU2022/000285 patent/WO2023048593A1/en active Application Filing
- 2022-09-19 EP EP22873266.5A patent/EP4411010A1/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023048593A1 (en) | 2023-03-30 |
| KR20240070638A (en) | 2024-05-21 |
| US20240247341A1 (en) | 2024-07-25 |
| CN117999374A (en) | 2024-05-07 |
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