CN110923589B - Short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 DEG C - Google Patents
Short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 DEG C Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 29
- 239000000835 fiber Substances 0.000 title claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 58
- 239000000956 alloy Substances 0.000 claims abstract description 58
- 239000000843 powder Substances 0.000 claims abstract description 14
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 238000005242 forging Methods 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 238000004663 powder metallurgy Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 20
- 238000005266 casting Methods 0.000 claims description 16
- 238000001513 hot isostatic pressing Methods 0.000 claims description 12
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 abstract description 7
- 230000002787 reinforcement Effects 0.000 abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 abstract description 7
- 229910052758 niobium Inorganic materials 0.000 abstract description 6
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 5
- 238000005495 investment casting Methods 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 238000002844 melting Methods 0.000 description 14
- 230000008018 melting Effects 0.000 description 14
- 238000005728 strengthening Methods 0.000 description 10
- 238000004321 preservation Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000000919 ceramic Substances 0.000 description 4
- 238000009689 gas atomisation Methods 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 210000003625 skull Anatomy 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910021332 silicide Inorganic materials 0.000 description 3
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 3
- 229910018125 Al-Si Inorganic materials 0.000 description 2
- 229910018520 Al—Si Inorganic materials 0.000 description 2
- 229910010967 Ti—Sn Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- 229910017305 Mo—Si Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910033181 TiB2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000009694 cold isostatic pressing Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/08—Making alloys containing metallic or non-metallic fibres or filaments by contacting the fibres or filaments with molten metal, e.g. by infiltrating the fibres or filaments placed in a mould
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
- C22C49/10—Refractory metals
- C22C49/11—Titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention aims to provide a short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 ℃, which comprises the following alloy components in percentage by mass: 5.0-7.0% of Al, 1.5-4.5% of Sn, 2.0-4.5% of Zr, 0.1-1.0% of Mo, 0.1-0.6% of Si, 0.1-0.8% of Nb, 0.1-1.8% of Ta, less than or equal to 0.08% of C, 0.1-1.2% of B, less than 0.3% of Fe, less than 0.15% of O, less than 0.05% of N, less than 0.012% of H and the balance of Ti and inevitable impurities. According to the invention, a proper amount of B element is added to realize TiB whisker short fiber reinforcement, and the content of Al, Mo, Si, Nb, Ta and other elements is regulated, so that the strength level is obviously improved, and the plasticity, toughness, high-temperature oxidation resistance and the like are considered. The alloy is suitable for forming methods such as forging, precision investment casting, powder metallurgy, laser powder additive manufacturing and the like.
Description
Technical Field
The invention belongs to the technical field of titanium alloy, and particularly relates to a short fiber reinforced high-temperature titanium alloy.
Background
The high-temperature titanium alloy is mainly applied to high-temperature bearing components of aerospace engines and aircrafts and is characterized by excellent high-temperature creep endurance, at present, the high-temperature titanium alloy which can be used at 600 ℃ mainly comprises British IMI834, American Ti1100, Russian BT36 and China Ti60 (national standard number TA33), and the newly developed Ti65 alloy (patent number ZL201410195990.9) can reach 650 ℃ in long-term use. In order to meet the development requirements of aerospace engines and aircrafts, the service temperature of a high-temperature structural part of the titanium alloy is continuously increased, the performance requirements of the conventional high-temperature titanium alloy are difficult to meet, and the development of a novel high-temperature titanium alloy with higher short-term service temperature and higher strength is urgently needed.
The existing high-temperature titanium alloys above 600 ℃ are all near-alpha type titanium alloys, the high-temperature strength and creep endurance performance of the high-temperature titanium alloys are ensured by adopting a mode of combining solid solution strengthening and second phase dispersion strengthening, the oxidation resistance of the high-temperature titanium alloys at high temperature is ensured in the component design, and the high-temperature titanium alloys of ZL200710011771.0 and ZL201410195990.9 are controlled by silicide and alpha2The heat strength of the alloy is improved, and proper amount of Nb and Ta are added, and the content of Mo element is controlled to improve the oxidation resistance of the alloy. In order to further increase the service temperature and the high-temperature strength, a new strengthening mode must be introduced. Researches show that the addition of B element in titanium alloy can obviously refine the casting structure, and is also beneficial to controlling the grain size in the subsequent thermal deformation process and realizing fine grain strengthening; the B element is mainly precipitated in the form of TiB whiskers in the titanium alloy, and the TiB whiskers can be pinned at grain boundaries by controlling the proper B element content and the processing technology, so that the fiber reinforcement effect is achieved. When B is added, the contents of Al, Si, Mo, Nb, Ta and other elements must be reasonably controlled, so that the strengthening mechanisms of solid solution strengthening, second phase strengthening, fiber strengthening and the like are comprehensively utilized, and ideal strong plasticity matching is obtained. However, there is no report of increasing the service temperature of the high temperature titanium alloy to 750 ℃ by using a TiB fiber reinforcement method.
Disclosure of Invention
The invention aims to provide a high-temperature titanium alloy capable of being used at 700-750 ℃, which realizes TiB whisker short fiber reinforcement by adding a proper amount of B element, regulates and controls the content of Al, Mo, Si, Nb, Ta and other elements, remarkably improves the strength level, and simultaneously considers plasticity, toughness, high-temperature oxidation resistance and the like. The alloy is suitable for forming methods such as forging, precision investment casting, powder metallurgy, laser powder additive manufacturing and the like.
The technical scheme is as follows:
a short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 ℃ is characterized in that the alloy comprises the following components in percentage by mass: 5.0-7.0% of Al, 1.5-4.5% of Sn, 2.0-4.5% of Zr, 0.1-1.0% of Mo, 0.1-0.6% of Si, 0.1-0.8% of Nb, 0.1-1.8% of Ta, less than or equal to 0.08% of C, 0.1-1.2% of B, less than 0.3% of Fe, less than 0.15% of O, less than 0.05% of N, less than 0.012% of H and the balance of Ti and inevitable impurities.
The alloy smelting process comprises the following steps:
the raw materials are sponge Ti, sponge Zr, pure Al, Ti-Sn intermediate alloy, Al-Mo intermediate alloy, Al-Si intermediate alloy, Al-Nb intermediate alloy, Ti-Ta intermediate alloy and TiB2Powder, C powder, TiO2And (3) mixing and blending the powder according to alloy components, pressing an electrode by using hydraulic equipment, assembling and welding the electrode, and performing vacuum consumable melting for 2-3 times to prepare an alloy ingot.
The hot isostatic pressing process of the casting, the powder metallurgy forming part and the powder additive manufacturing forming part comprises the following steps: (920-940) DEG C/120-140 MPa/(2-3) h/furnace cooling.
The forging piece adopts solution aging heat treatment, and the specific process comprises the following steps: t isβAir cooling or air cooling at (-10-40) DEG C/2 h or oil quenching at + (600-750) DEG C/5 h/air cooling.
The alloy is a near-alpha type high-temperature titanium alloy based on Ti-Al-Sn-Zr-Mo-Si system, the addition of B element can precipitate TiB crystal whisker to realize short fiber reinforcement, and meanwhile, the alloy has the function of refining crystal grains to realize fine grain reinforcement, the reinforcement effect is enhanced along with the increase of B content, but the excessively high B content can cause the alloy plasticity to be obviously reduced, and the mass fraction is controlled not to exceed 1.2%.
B and Al, Mo, Si, Nb, Ta and other elements play different strengthening effects, and can be matched according to specific requirements to obtain the optimal strong plasticity matching. Al is the most main alpha stable element, and an alpha 2 phase is precipitated after the solubility limit of the Al exceeds the solubility limit of the Al in the alpha phase, so that the high-temperature strength and the creep resistance of the alloy can be obviously improved, but the alloy becomes brittle due to excessive alpha 2 phase, and the mass fraction of the Al is controlled not to exceed 7% by combining the short fiber reinforcing effect of TiB whiskers; si is an important strengthening element in high temperature titanium alloys and can form (Ti, Zr, Sn)5Si3Or (Ti, Zr, Sn)6Si3The silicide can obviously improve the high-temperature strength and the lasting creep property of the alloy, but excessive Si can cause the plasticity of the alloy to be reduced, so the mass fraction of the silicide is controlled not to exceed 0.6 percent; mo is a main beta stable element, can improve the processing property of the alloy, is beneficial to the thermal stability of the alloy, but has overhigh Mo elementThe oxidation resistance of the alloy is reduced due to the element content, and the mass fraction of the alloy in the near-alpha high-temperature titanium alloy is generally controlled to be lower than 1.0 percent; nb and Ta are isomorphous beta stable elements, so that an oxide layer on the surface of the alloy can be more compact, uniform and fine, the adhesion between an oxide film and a matrix interface is increased, and the high-temperature oxidation resistance of the high-temperature titanium alloy is obviously improved, so that the mass fraction of Nb is controlled to be 0.1-0.8%, and the mass fraction of Ta is controlled to be 0.1-1.8%.
Compared with the existing high-temperature titanium alloy, the invention has the following advantages:
firstly, the alloy has good formability and can be formed by adopting methods such as investment casting, forging, powder metallurgy, laser powder additive manufacturing and the like.
And secondly, introducing a TiB short fiber reinforcing mechanism, and matching with Al, Si, Mo, Nb, Ta and other elements, wherein the alloy can be used at 700-750 ℃, and compared with the alloy without B element, the strength of the alloy component and the use temperature are obviously improved.
After castings, powder metallurgy formed parts and powder additive manufacturing formed parts are subjected to cold and hot isostatic pressing treatment at 920-940 ℃ and 120-140 MPa/(2-3) h/furnace, the yield strength at room temperature is not lower than 960MPa, the tensile strength is not lower than 1060MPa, and the elongation is not lower than 5%; the yield strength is not lower than 450MPa at 700 ℃, the tensile strength is not lower than 580MPa, and the elongation is not lower than 10%; the yield strength at 750 ℃ is not lower than 380MPa, the tensile strength is not lower than 470MPa, and the elongation is not lower than 10%.
Forging and warp beam T thereofβAfter heat treatment at the temperature of (10-40) DEG C/2 h/air cooling or oil quenching + (600-750) DEG C/5 h/air cooling, the yield strength at room temperature is not lower than 1060MPa, the tensile strength is not lower than 1160MPa, and the elongation is not lower than 5%; the yield strength is not lower than 470MPa at 700 ℃, the tensile strength is not lower than 600MPa, and the elongation is not lower than 12%; the yield strength at 750 ℃ is not lower than 400MPa, the tensile strength is not lower than 490MPa, and the elongation is not lower than 12%.
Detailed Description
The alloy ingot preparation methods of the comparative example and the example were:
sponge Ti, sponge Zr, pure Al, Ti-Sn intermediate alloy, Al-Mo intermediate alloy, Al-Si intermediate alloy, Al-Nb intermediate alloy, Ti-Ta intermediate alloy and C powder are mixed uniformly and pressed into an electrode, and after the electrode is welded, alloy ingot casting is obtained through vacuum consumable melting for 2-3 times. The main chemical composition of each alloy ingot is shown in table 1.
Table 1 alloy composition (wt.%)
Alloy (I) | Al | Sn | Zr | Mo | Si | Nb | Ta | C | B | Fe | O | N | H |
1# | 5.87 | 4.02 | 3.5 | 0.68 | 0.32 | 0.44 | 0.46 | 0.06 | 0.015 | 0.07 | 0.012 | 0.003 | |
2# | 5.85 | 3.94 | 3.42 | 0.7 | 0.37 | 0.41 | 0.43 | 0.05 | 0.65 | 0.018 | 0.09 | 0.01 | 0.003 |
3# | 5.5 | 2.8 | 2.75 | 0.77 | 0.58 | 0.18 | 1.2 | 0.02 | 1.08 | 0.011 | 0.1 | 0.01 | 0.002 |
4# | 6.5 | 2.55 | 2.35 | 0.15 | 0.18 | 0.15 | 0.16 | 0.06 | 0.88 | 0.012 | 0.09 | 0.008 | 0.003 |
Comparative example 1
And melting the cast ingot of the No. 1 alloy in a vacuum consumable electrode skull furnace, casting, wherein the used mould shell is a ceramic mould, cooling, demoulding, hot isostatic pressing the casting at 930 ℃ and 130MPa for 2.5h, and then furnace cooling.
Example 1:
and melting the cast ingot of the 2# alloy in a vacuum consumable electrode skull furnace, casting, wherein the used mould shell is a ceramic mould, cooling, demoulding, hot isostatic pressing the casting at 930 ℃ and 130MPa for 2.5h, and then furnace cooling.
Example 2:
and melting the 3# alloy cast ingot in a vacuum consumable electrode skull furnace, casting, wherein the used mould shell is a ceramic mould, cooling, demoulding, hot isostatic pressing the casting at 920 ℃ and 140MPa for 3h, and then furnace cooling.
Example 3:
and 4# alloy cast ingot is melted in a vacuum consumable electrode skull furnace and then cast, the used mould shell is ceramic, after cooling and demoulding, the casting is cooled along with the furnace after hot isostatic pressing for 2.5h at 940 ℃ and 140 MPa.
The mechanical property pair ratios of different alloy castings are shown in table 1:
TABLE 1 comparison of mechanical properties of comparative example 1 and examples 1-3
Comparative example 2:
the 1# alloy ingot is cogging in a beta single-phase region, is forged into a bar with the diameter of 70mm in an alpha + beta two-phase region, is subjected to oil quenching after being subjected to heat preservation at 1015 ℃ for 2h, and is subjected to heat preservation at 700 ℃ for 5h and then is subjected to air cooling.
Example 4:
and 2# alloy ingot casting is cogging in a beta single-phase region, is forged into a bar with the diameter of 70mm in an alpha + beta two-phase region, is subjected to oil quenching after being subjected to heat preservation at 1025 ℃ for 2h, and is subjected to heat preservation at 700 ℃ for 4h and then is subjected to air cooling.
Example 5:
and 3# alloy ingot casting is cogging in a beta single-phase region, is forged into a bar with the diameter of 45mm in an alpha + beta two-phase region, is subjected to oil quenching after heat preservation at 1015 ℃ for 1.5h, and is subjected to air cooling after heat preservation at 700 ℃ for 3.5 h.
Example 6:
the 4# alloy cast ingot is cogging in a beta single-phase region, is forged into a bar with the diameter of 90mm in an alpha + beta two-phase region, is subjected to oil quenching after being subjected to heat preservation at 1015 ℃ for 2h, and is subjected to heat preservation at 700 ℃ for 5h and then is subjected to air cooling.
The mechanical property pair ratios of different alloy forging bars are shown in table 2:
TABLE 2 comparative example 2 compares tensile properties with examples 4-6
Comparative example 3:
the method comprises the following steps of cogging a No. 1 alloy ingot in a beta single-phase region, forging the ingot into a bar, then preparing powder by crucible-free induction melting gas atomization, preparing a plate-shaped sample by a selective laser melting additive manufacturing technology, and carrying out 930 ℃/130MPa/2.5 h/furnace cold hot isostatic pressing treatment on the sample.
Example 7:
cogging a No. 2 alloy ingot in a beta single-phase region, forging the ingot into a bar, then preparing powder by crucible-free induction melting gas atomization, preparing a plate-shaped sample by a selective laser melting additive manufacturing technology, and performing 930 ℃/130MPa/2.5 h/furnace cold hot isostatic pressing treatment on the sample.
Example 8:
cogging a 3# alloy ingot in a beta single-phase region, forging the ingot into a bar, then preparing powder by crucible-free induction melting gas atomization, preparing a plate-shaped sample by a laser selective melting additive manufacturing technology, and carrying out 920 ℃/140MPa/3 h/furnace cold hot isostatic pressing treatment on the sample.
Example 9:
cogging a 4# alloy ingot in a beta single-phase region, forging the ingot into a bar, then preparing powder by crucible-free induction melting gas atomization, preparing a plate-shaped sample by a selective laser melting additive manufacturing technology, and carrying out 940 ℃/130MPa/2.5 h/furnace cold hot isostatic pressing treatment on the sample.
The mechanical property pair ratios of different alloy laser selective melting additive manufacturing samples are shown in table 3:
TABLE 3 comparison of tensile Properties of comparative example 3 with examples 7-9
The invention is not the best known technology.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (2)
1. A short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 ℃ is characterized in that the alloy comprises the following components in percentage by mass: 5.5-6.5% of Al, 2.55-4.5% of Sn, 2.35-4.5% of Zr, 0.15-1.0% of Mo, 0.1-0.6% of Si, 0.15-0.8% of Nb, 0.16-1.8% of Ta, less than or equal to 0.08% of C, 0.1-1.2% of B, less than 0.3% of Fe, less than 0.15% of O, less than 0.05% of N, less than 0.012% of H and the balance of Ti and inevitable impurities;
the hot isostatic pressing process is adopted to prepare a high-temperature titanium alloy casting, a powder metallurgy forming part and a powder additive manufacturing forming part, and the specific process parameters are as follows: keeping the temperature at 920-940 ℃ and 120-140 MPa for 2-3 h, and cooling the furnace; the yield strength of the casting, the powder metallurgy forming piece and the powder additive manufacturing forming piece after the hot isostatic pressing treatment is not lower than 450MPa at 700 ℃, the tensile strength is not lower than 580MPa, and the elongation is not lower than 10%; the yield strength at 750 ℃ is not lower than 380MPa, the tensile strength is not lower than 470MPa, and the elongation is not lower than 10%.
2. A short fiber reinforced high-temperature titanium alloy Ti-101AM for 700-750 ℃ is characterized in that the alloy comprises the following components in percentage by mass: 5.5-6.5% of Al, 2.55-4.5% of Sn, 2.35-4.5% of Zr, 0.15-1.0% of Mo, 0.1-0.6% of Si, 0.15-0.8% of Nb, 0.16-1.8% of Ta, less than or equal to 0.08% of C, 0.1-1.2% of B, less than 0.3% of Fe, less than 0.15% of O, less than 0.05% of N, less than 0.012% of H and the balance of Ti and inevitable impurities;
the high-temperature titanium alloy forging adopts solution aging heat treatment, and the specific process comprises the following steps: tbeta- (10-40) DEG C/2 h/air cooling or oil quenching + (600-750) DEG C/5 h/air cooling; after the forging is subjected to solution aging heat treatment, the yield strength at 700 ℃ is not lower than 470MPa, the tensile strength is not lower than 600MPa, and the elongation is not lower than 12%; the yield strength at 750 ℃ is not lower than 400MPa, the tensile strength is not lower than 490MPa, and the elongation is not lower than 12%.
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