巴西专利BR112016011895B1 FOREIGNABLE ALLOY OF NICKEL-CHROME-COBALT-TITANIUM-ALUMINUM HARDENER, THESE USES

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专利摘要:
The present invention relates to a hardenable nickel-chromium-cobalt-titanium-aluminum alloy, with very good wear resistance, and at the same time very good corrosion resistance at high temperatures, good creep resistance and good processability , with (in mass%)> 18 to 31% by weight of chromium, 1.0 to 3.0% of titanium, 0.6 to 2.0% of aluminum,> 3.0 to 40% of cobalt, 0.005 to 0.10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, max. 0.10% sulfur, max. 0.020% oxygen, max. 0.70% silicon, max. 2.0% manganese, max. 0.05% magnesium, max. 0.05% calcium, max. 2.0 molybdenum, max. 2.0% tungsten, max. 0.5% niobium, max. 0.5% copper, max. 0.5% vanadium, if necessary, 0 to 20% Fe, if necessary, 0 to 0.20% Zr, if necessary, 0.0001 to 0.008% boron, remaining nickel and the usual impurities, resulting from process, with the nickel content being greater than 35%, and the Cr + Fe + Co ¿25% (1) ratio needs to be met to obtain good wear resistance and the fh ¿0 (2a) ratio, with fh = 6.49 +3.88 Ti - 1.36 Al? 0.301 Fe + (0.759? 0.0209 Co) Co-0.428 Cr? 28.2 C (2) must be satisfied, so that there is sufficient resistance to higher temperatures, with Ti, Al, Fe, Co, Cr and C being the concentration of the corresponding elements in mass% and fh is indicated in %.
公开号:BR112016011895B1
申请号:R112016011895-2
申请日:2015-01-12
公开日:2021-02-23
发明作者:Heike Hattendorf
申请人:Vdm Metals International Gmbh；
IPC主号:

专利说明:

[0001] The invention relates to a nickel-chromium-cobalt-titanium-aluminum alloy, with very good wear resistance, to very good creep resistance, good resistance to corrosion at high temperatures, and good processability.
[0002] Austenitic nickel, chromium-titanium-aluminum alloys, endowed with different levels of nickel, chromium, titanium and aluminum, have long been used for engine discharge valves. Good wear resistance, good thermal resistance / creep resistance, good alternative resistance, as well as good resistance to corrosion at high temperatures (particularly in exhaust gases) are required for this use.
[0003] The document DIN EN 10090 mentions for discharge valves, in particular, austenitic alloys, of which the nickel alloys 2.4955 and 2.4952 (NiCr20TiAl) have the highest thermal and creep resistances of all the alloys mentioned in this standard . Table 1 shows the composition of the nickel alloys mentioned in the document DIN EN 10090, Tables 2 to 4 show the tensile strengths, the elongation limit of 0.2% and the guideline values for creep strength after 1,000 H.
[0004] The document DIN EN 10090 mentions two alloys with a high nickel content: a) NiFe25Cr20NbTi, with 0.05 - 0.10% C, max. 1.0% Si, max. 1.0% Min, max. 0.030% P, max. 0.015% S, 18.00 to 21.00 Cr, 23.00 to 28.00% Fe, 0.30 -1.00% Al, 1.00 to 2.00% Ti, 1, 00 - 2nd Nb + Ta, max. 0.008% of B and remainder, Ni. b) NCr20TiAl with 0.05 - 0.10% C, max. 1.0% Si, max. 1.0% Mn, max. 0.020% P, max. 0.015% S, 18.00 to 21.00% Cr, max. 3% Fe, 1.00 - 1.80% Al, 1.80 - 2.70% Ti, max. 0.2% Cu max. 0.008% of B and remainder, Ni.
[0005] NiCr20TiAl has, in comparison with NiFe 25Cr20NbTi, tensile strengths, 0.2% elongation limits and markedly higher creep resistances at elevated temperatures.
[0006] EP 0 639 654 A2 describes a ferro-nickel-chromium alloy, consisting of (in% by weight) up to 0.15% C, up to 1.0% Si, up to 3.0% of Mn, 30 to 49% of Ni, 10 to 18% of Cr, 1.6 to 3.0% of Al, one or more elements from group IVa to Va with a total content of 1.5 to 8.0% , remainder, Fe and unavoidable impurities, where Al is an indispensable additive element and one or more elements from group IVa to Va already mentioned, must satisfy the following formula in% in atoms: 0.45 <Al / (Al + Ti + Zr + Hf + V + Nb + TA) <0.75.
[0007] WO 2008/007190 describes a wear-resistant alloy, consisting of (in% by weight) 0.15 to 0.35% C, up to 1.0% Si, up to 1.0% Mn,> 25 to <40% Ni, 15 to 25% Cr, up to 0.5% Mo, up to 0.5% W,> 1.6 to 3.5% Al,> 1, 1% to 3% in the sum Nb + Ta, up to 0.015% of B, remainder, Fe and unavoidable impurities, with Mo + 0.5W <0.75%; Ti + Nb> 4.5% and 13 <(Ti + Nb) / C <50. The alloy is particularly useful for the production of discharge valves for internal combustion engines. The good wear resistance of this alloy is based on the high proportion of primary carbides, which are formed due to the high carbon content. A high proportion of carbides, however, causes processing problems in the production of this alloy as a forged alloy.
[0008] In all the aforementioned alloys, the thermal resistance or resistance to creep in the range of 500 ° C to 900 ° C is based on the addition of aluminum, titanium and / or niobium (or other elements, such as Ta ,. ..), which lead to the separation of the y 'and / or y "phase. In addition, thermal resistance or creep resistance are also improved by high element levels, which increase the resistance of mixed crystals, such as chromium , aluminum, silicon, molybdenum and tungsten, as well as for a high carbon content.
[0009] Regarding resistance to corrosion at elevated temperatures, it should be noted that alloys with a chromium content around 20% form a protective chromium oxide (Cr2O3) layer of the material. The chromium content is slowly consumed during use in the application area to form the protective layer. For this reason, due to a higher chromium content, the useful life of the material is improved, since a higher content of the chromium element, which forms the protective layer, postpones the moment when the Cr content is below the critical limit and oxides other than Cr2O3 are formed, which are, for example, oxides containing cobalt and nickel.
[00010] For processing the alloy, particularly in hot shaping, it is necessary that at temperatures at which hot shaping occurs, no phases are formed, which strongly reinforce the strength of the material, such as, for example, the y 'phase. or y "and thereby lead to the formation of a crack in hot forming. At the same time, these temperatures must be sufficiently below the solid temperature of the alloy to avoid melting in the alloy.
[00011] EP 1 696 108 A1 describes a heat resistant alloy for exhaust gas valves, which has the following composition: 0.01-0.15% C, up to 2.0% Si, up to 1, 0% Mn, up to 0.02% P, up to 0.01% S, 0.1 - 15% Co, 15-25% Cr, 0.1-10% Mo and / or 0, 1-5% of W, the sum of Mo + ^ W should be 3 -10%, 1.0-3.0% of Al, 2.0 - 3.5 of Ti, with the sum of Al + Ti (in% in atoms) must be 6.3 - 8.5% and the ratio of Ti to Al must be 0.4 - 0.8. In addition, elements B still occur at levels of 0.001 - 0.091%, Fe up to 3.0%, remainder, nickel and unavoidable impurities.
[00012] EP 1 464 718 A1 refers to a highly resistant, heat resistant alloy for exhaust gas valves, with the following chemical composition: 0.01-0.2% C, up to 1.0% Si, up to 1.0% Mn, up to 0.02% P, up to 0.01% S, 30 - 62% Ni, 1320% Cr, up to 2.0% Mo, 0.01 -3.0 %% of W, and the sum of Mo + 0.5 W should make up 1.0 -2.5%,> 0.7 - <1.6% De Al, 1.5 - 3, 0% Ti, the ratio of Ti to Al should be> 1.6 - <2.0, 0.5 - 1.5% Nb, 0.001 - 0.01 of the rest, Fe and unavoidable impurities.
[00013] WO 2013/182178 A1 describes a nickel-chromium alloy, with good processability, creep resistance and corrosion resistance, which has the following composition: 29-37% Cr, 0.001 - 1.8% Al, 0.1 - 7.0% Fe, 0.001 - 0.005% Mg and / or Ca, 0.005 - 0.12% C, 0.001 - 0.05% N, 0.001 - 0.03% P, 0.001 - 0.02% O, max. 0.01% S, max. 2.0% Mo, max. 2.0% of W, remaining nickel and the usual impurities resulting from the process.
[00014] The task on which the invention is based is to create a forging nickel-chromium alloy, which features: • better wear resistance than NiCr20TiAl; • a thermal resistance / creep resistance similarly good to NiCr20TiAl; • good resistance to corrosion such as NiCr20TiAl; and • good processability equivalent to that of NiCr20TiAl.
[00015] This task is solved by a forging nickel-chromium-cobalt-titanium-aluminum alloy, with very good wear resistance, with, at the same time, a very good creep resistance, very good corrosion resistance at very high temperatures, and good processability, with (% by mass)> 18 to 26% by weight of chromium, 1.5 to 3.0% of titanium, 0.6 to 2.0% of aluminum, 5.0 to 40% cobalt, 0.005 to 0.10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, max. 0.10% sulfur, max. 0.020% oxygen, max. 0.70% silicon, max. 2.0% manganese, max. 0.05% magnesium, max. 0.05% calcium, max. 0.5 molybdenum, max. 0.5% tungsten, max. 0.2% niobium, max. 0.5% copper, max. 0.5% vanadium, if necessary, 0 to 20% Fe, if necessary, if necessary, 0 to 0.20% Zr, if necessary, 0.0001 to 0.008% boron, and, optionally, still The following elements in the alloy may be contained: Y 0 - 0.20% and / or La 0 - 0.20% and / or Ce 0 - 0.20% and / or Mixed metal of cerium 0 - 0.20% and / or Hf 0 - 0.20% and / or Ta 0 - 0.60%
[00016] Remaining nickel and the usual impurities are due to the process, adjusted to the contents of, max. 0.002% Pb, max. 0.002% Zn, max; 0.002% of Sn, the nickel content being greater than 35%, and the following ratios need to be satisfied; Cr + Fe + Co> 25% (1) to obtain good wear resistance, and fh> 0 with (2a) fh = 6.49 +3.88 Ti + 1.36 Al - 0.301 / Fe + (0.759 - 0.0209 Co) Co-0.428 Cr - 28.2 C, (2) to obtain sufficient resistance at elevated temperatures, with T, Al, Fe, Co, Cr and C being the concentration of the corresponding elements in% by mass and fh is indicated in%.
[00017] Advantageous improvements to the object of the invention can be found in the corresponding secondary claims.
[00018] The extension range for the chromium element is between> 18 and 26%, with preferred scopes being adjustable as follows: -> 18 to 25% - 19 to 24% - 19 to 22%
[00019] The titanium content is between 1.5 and 3.0%. Preferably, Ti can be adjusted within the scope of extension in the alloy as follows: - 1.8 - 3.0% - 2.0 - 3.0% - 2.2 - 3.0% - 2.2 - 2.8%
[00020] The aluminum content is between 0.6 and 2.0%, and here too, depending on the area of use of the alloy, preferred aluminum levels can be adjusted, as follows; - 0.9 to 2.0% - 1.0 to 2.0% - 1.2 to 2.0%
[00021] The scope of cobalt is between 5.0 and 40%, and, depending on the application area, preferred levels can be adjusted within the following scope of extension: - 5.0 - 35% - 9.0 - 35 % - 12.0 - 35% - 15.0 - 35% - 20.0 - 35% - 20.0 - 30%
[00022] The alloy contains 0.005 to 0.10% carbon. Preferably, it can be adjusted within the scope of extension in the alloy as follows: - 0.01 - 0.10% - 0.02 - 0.10% - 0.04 - 0.10% - 0, 04 - 0.08%
[00023] This is the same for the element nitrogen, which is contained in levels between 0.0005 and 0.05%. Preferred contents can be present as follows: - 0.001 - 0.05% - 0.001 - 0.04% - 0.001 - 0.03% - 0.001 - 0.02% - 0.001 - 0.01%
[00024] The alloy also contains phosphorus, in levels between 0.0005 and 0.030. Preferred contents can be presented as follows: - 0.001 - 0.030% - 0.001 - 0.020%
[00025] The sulfur element is present in the alloys as follows: - max. 0.010%
[00026] The oxygen element is contained in the alloy in max. 0.020%. Other preferred levels can be presented as follows: - max. 0.010% - max. 0.008% - max. 0.004%
[00027] The Si element is contained in the alloy in max. 0.70%. Other preferred levels can be presented as follows: - max. 0.50% - max. 0.20% - max. 0.10%
[00028] In addition, the Mn element is contained in the alloy in contents of max. 2.0%. Other preferred levels can be presented as follows: - max. 0.60% - max. 0.20% - max. 0.10%
[00029] The element Mg is contained in the alloy in contents of max. 0.05%. Other preferred levels can be presented as follows: - max. 0.04% - max. 0.03% - max. 0.02% - max. 0.01%
[00030] The Ca element is contained in the alloy in max. 0.05%. Other preferred levels can be presented as follows: - max. 0.04% - max. 0.03% - max. 0.02% - max. 0.01%
[00031] The niobium element is contained in the alloy in contents of max. 0.2%. Other preferred levels can be presented as follows: - max. 0.10% - max. 0.05%
[00032] Molybdenum and tungsten are contained in the alloy, individually or in combination, with a content of, in each case, a maximum of 2.0%. Preferred contents can be presented as follows: - Mo <0.10% - W <0.10% - Mo <0.05% - W <0.05%
[00033] In addition, a maximum of 0.5% Cu may be contained in the alloy. The copper content can furthermore be limited as follows: - Cu <0.10% - Cu <0.05% - Cu <0.015%
[00034] In addition, a maximum of 0.5% vanadium may be contained in the alloy.
[00035] In addition, the alloy can contain, if necessary, between 0.0 and 20.0% iron, which, in addition, can still be limited as follows: -> 0 to 15.0% -> 0 to 12.0% -> 0 to 9.0% -> 0 to 6.0% -> 0 to 3.0%
[00036] In addition, the alloy, if necessary, can contain between 0 and 0.20% zirconium, which, in addition, can still be limited as follows: - 0.01 - 0.20% - 0, 01 - 0.15% - 0.01 - <0.10%
[00037] In addition, the alloy, if necessary, can contain between 0.0001 - 0.008% of boron. Other preferred levels can be presented as follows: - 0.0005 - 0.006% - 0.0005 - 0.004%
[00038] The nickel content must be above 35%. Preferred levels can be presented as follows: -> 40% -> 45% -> 50%
[00039] The following relationship between Cr and Co and Fe needs to be satisfied, so that there is sufficient resistance against wear: Cr + CO + Fe> 25% (1) with Cr, Co and Fe being the concentration of the corresponding elements in % in large scale.
[00040] Other preferred ranges can be adjusted with Cr + Co + Fe> 26% (1a) Cr + Co + Fe> 27% (1b) Cr + Co + Fe> 28% (1c) Cr + Co + Fe> 30 % (1d) Cr + Co + Fe> 35% (1e) Cr + Co + Fe> 40% (1f)
[00041] The following relationship between Ti, Al, Fe, Co, Cr and C needs to be satisfied, so that there is a sufficiently high resistance at higher temperatures: fh> 0 with (2a) fh = 6.49 + 3.88 Ti + 1.36 Al - 0.301 Fe + (0.759 - 0.0209 Co) Co 0.428 Cr - 28.2 C (2) with Ti, Al, Fe, Co, Cr and C being the concentration of the corresponding elements in % by mass and fh is indicated in%.
[00042] Preferred scopes can be adjusted with fh> 1% (2b) fh> 3% (2c) fh> 4% (2d) fh> 5% (2e) fh> 6% (2f) fh> 7% (2g )
[00043] Optionally, the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb can be satisfied in the alloy, so that there is sufficiently good processability: fver = <7 with (3a) fver = 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0.0109 Fe) Co + 40.67 Ti * Al + 33.28 Al2 - 13.6 TiAl2 - 22.99 Ti - 92.7 Al + 2.94 Nb, (3)
[00044] where Cr, Mo, W. Fe, Co, Ti, Al and Nb are the concentration of the corresponding elements in% by mass and fver is indicated in%. Preferred scopes can be adjusted with fver = <5% (3b) fver = <3% (3c) fver = <0% (3d)
[00045] Optionally, the yttrium element can be adjusted in the alloy in levels from 0, .0 to 0.20. Preferably, Y can be adjusted on the alloy within the scope of extension, as follows: - 0.01 - 0.20% - 0.01 - 0.15% - 0.01 - 0.10% - 0, 01 - 0.08% - 0.01 - <0.045%
[00046] Optionally, the lanthanum element can be adjusted in the alloy in levels from 0, .0 to 0.20. Preferably, La can be adjusted on the alloy within the scope of extension, as follows: - 0.001 - 0.20% - 0.001 - 0.15% - 0.001 - 0.10% - 0.001 - 0.08% - 0.001 - 0.04% - 0.01 - 0.04%
[00047] Optionally, the Ce element can be adjusted in the alloy in levels from 0, .0 to 0.20. Preferably, Ce can be adjusted on the alloy within the scope of extension, as follows: - 0.001 - 0.20% - 0.001 - 0.15% - 0.001 - 0.10% - 0.001 - 0.08% - 0.001 - 0.04% - 0.01 - 0.04%
[00048] Optionally, with a simultaneous addition of Ce and La, mixed cerium metal can also be used, in levels of 0.0 to 0.20%. Preferably, mixed cerium metal can be adjusted on the alloy within the scope of extension, as follows: - 0.001 - 0.20% - 0.001 - 0.15% - 0.001 - 0.10% - 0.001 - 0.08 % - 0.001 - 0.04% - 0.01 - 0.04%
[00049] Optionally, the alloy can also contain 0.0 to 0.20% hafnium. Preferred scopes can be presented as follows: - 0.001 - 0.20% - 0.001 - 0.15% - 0.001 - 0.10% - 0.001 - 0.08% - 0.001 - 0.04% - 0.01 - 0.04%
[00050] Optionally, the alloy can also contain 0.0 to 0.60% tantalum. - 0.001 - 0.60% - 0.001 - 0.40% - 0.001 - 0.20% - 0.001 - 0.15% - 0.001 - 0.10% - 0.001 - 0.08% - 0.001 - 0.04% - 0.01 - 0.04%
[00051] Finally, in impurities, the elements lead, zinc and tin can still be present, in contents, as follows: Pb max 0.002% Zn max 0.002% Sn max 0.002%
[00052] The alloy according to the invention is preferably melted in the vacuum induction oven (VIM), but it can also be melted open, followed by a treatment in a VOD or VLF installation. After block casting or, optionally, as an extrusion, the alloy is optionally annealed at temperatures between 600 ° C and 1100 ° C for 0.1 hour (h) to 100 hours, optionally under shielding gas, such as , for example, argon or oxygen, followed by cooling in air or in the moved annealing atmosphere. Then, a re-melting can be done using VAR or ESU, optionally followed by a 2nd re-melting process via VAR or ESU. Then the blocks are annealed, optionally, at temperatures between 900 ° C and 1,270 ° C for 0.1 to 70 hours, then heat-transformed, optionally with one or more intermediate anneals between 900 ° C and 1270 ° C for 0, 05 hours up to 70 hours. Hot processing can take place, for example, by forging or hot rolling. The material surface can be removed during the entire process, optionally (also several times), during and / or at the end.
[00053] The alloy according to the invention is preferably melted in the vacuum induction oven (VIM), but it can also be melted open, followed by a treatment in a VOD or VLF installation. After block casting or, optionally, as an extrusion, the alloy is optionally annealed at temperatures between 600 ° C and 1100 ° C for 0.1 to 100 hours, optionally under shielding gas, such as, for example, argon or oxygen, followed by cooling in air or in the moved annealing atmosphere. Then, a re-melting can be done using VAR or ESU, optionally followed by a 2nd re-melting via VAR or ESU. Then the blocks are annealed, optionally at temperatures between 900 ° C and 1,270 ° C for 0.1 to 70 hours, then heat-transformed, optionally with one or more intermediate anneals between 900 ° C and 1270 ° C for 0.05 hours up to 70 hours. Hot processing can take place, for example, by forging or hot rolling. The surface of the material can be removed during the entire process, optionally (also several times), during and / or at the end, for cleaning, chemically (for example, by pickling) and / or mechanically (for example, by lifting chips, by sandblasting or grinding). The hot shaping process can be carried out in such a way that the semi-cabled product is then recrystallized with particle sizes between 5 and 100 μm, preferably between 5 and 40 μm. Optionally, annealing occurs in solution at a temperature range of 700 ° C to 1270 ° C for 0.1 min up to 70 hours, optionally under shielding gas, such as, for example, argon or oxygen, followed by cooling air in the moved annealing atmosphere or in the water bath. After the end of the hot shaping, cold shaping (for example, laminating, drawing, hammering, stamping, pressing) can optionally be carried out, with degrees of transformation of up to 98% to the desired shape of the semi-finished product, optionally, with intermediate anneals between 700 ° C and 1270 ° C for 0.1 min and 70 hours, optionally under shielding gas, such as, for example, argon or oxygen, followed by air cooling in the moved annealing atmosphere or in the bath of water. Optionally, during the cold forming process and / or after the last annealing, chemical and / or mechanical cleaning (for example, sandblasting, grinding, turning, scraping, brushing) of the material surface occurs.
[00054] The alloys according to the invention or the parts produced therefrom obtain the definitive properties by hardening annealing between 600 ° C and 900 ° C for 0.1 to 300 hours, followed by air cooling and / or in the oven. By such a hardening annealing the alloy according to the invention is hardened by separating a finely divided y-phase. Alternatively, annealing can also take place in two stages, in which the first annealing takes place within the range of 800 ° C to 900 ° C for 0.1 to 300 hours, followed by air cooling and / or cooling in the oven, and a second annealing between 600 ° C and 800 ° C for 0.1 to 300 hours, followed by air cooling.
[00055] The alloy according to the invention can be well produced and used in the product forms tape, plate, bar, wire, welded tube with longitudinal seam and seamless tube.
[00056] These product forms are produced with an average particle size of 3 μm to 600 μm. The preferred range is between 5 μm and 70 μm, particularly between 5 and 40 μm.
[00057] The alloy according to the invention can be processed appropriately by means of forging, settlement, hot extrusion, hot rolling or similar processes. Through these processes, components such as valves, hollow valves or pins can be produced, among others.
[00058] The alloy according to the invention should preferably be used in areas for valves, particularly discharge valves for internal combustion engines. However, it is also possible to use it in gas turbine components such as spring clamping pins and in turbochargers.
[00059] Parts produced from the alloy according to the invention, particularly, for example, valves or valve seat areas, can be subjected to other surface treatments, such as, for example, nitration, to increase additionally wear resistance. Tests
[00060] For wear resistance measurement, slip wear tests were performed on a pin (pin) disk test post (Optimal SRV IV tribometer). The radius of the semi-spherical pins, polished in the manner of a mirror, amounted to 5mm. The pins were produced from the material to be tested. The disc consisted of cast iron with an annealed martensitic matrix, with secondary carbides, within an eutectic carbide network, with the composition (C «1.5%, Cr« 6%, S «0.1%, Mn« 1 %, Mo «9%, Si« 1.5%, V «3%, Fe rest.) The tests were carried out at a load of 20 N, with a sliding path of one mm, a frequency of 20 Hz and an air humidity of about 45%, at different temperatures. Details of the tribometer and the test procedure are described in „C. Rynio, H. Hattendorf, J. Klower, H.-G. Lüdecke, G. Eggeler, Mat.-wiss. u. Werkstofftech. 44 (2013) ". During the test, the friction coefficient, the linear displacement of the pin in the direction of the disc (as a measure for the total linear wear of the pin and disc) and the electrical contact resistance between pin and disc are continuously measured The measurement was made with 2 different force measurement modules, which are then designated as (a) or (n). They provide slightly different results quantitatively, but similar qualitatively. The force measurement module ( n) is the most accurate, after the end of a test, the volume loss of the pin was measured and used as a measure for the classification of the wear resistance of the pin material.
[00061] The thermal resistance was determined in a hot tensile test according to DIN EN ISO 6892-2. In this case, the elongation limit Rp0.2 and the tensile strength Rm were determined: The tests were carried out on round samples, with a diameter of 6 mm in the measurement area and an initial measurement length L0 of 30 mm. The sample was taken across the transformation direction of the semi-finished product. The transformation rate was Rp0.2 8.33 10-5 1 / s (0.5% / min) and Rm 8.33 10-4 1 / s (5% / min).
[00062] The sample was assembled at room temperature in a tensile testing machine and heated to the desired temperature, without load, with a tensile force. After reaching the test temperature, the sample was kept, without load, for one hour (600 ° C) or two hours (700 ° C to 1100 ° C) for temperature regulation. Then, the sample was loaded with a tensile force, in such a way that the stretching speeds were maintained and the test was started.
[00063] The creep resistance of a material is improved with increasing thermal resistance. For this reason, thermal resistance is also used to assess the creep resistance of different materials.
[00064] Resistance to corrosion at elevated temperatures was determined in an oxidation test, in air, at 800 ° C, the test being interrupted every 96 hours and the mass changes of the samples by oxidation were determined. The samples were placed in a ceramic crucible, so that optionally chipped oxide was collected and by weighing the path containing the oxides, the mass of the chipped oxide can be determined. The sum of the mass of the chipped oxide and the mass modification of the sample is the gross mass modification of the sample. The specific mass modification is the mass modification referred to the surface of the samples. They are designated hereinafter by mneto, for the modification of specific net mass, mbruto, for the modification of specific gross mass, mspall, for the modification of chipped oxides. The tests were performed on samples with a thickness of about 5 mm. From each load, 3 samples were hardened, the indicated values are the average values of those 3 samples.
[00065] The phases that are presented in equilibrium, were calculated for the various alloy variants with the Thermotech JMatPro program. As a database for the calculations, the TNI7 database for Thermotech nickel-based alloys was used. Thus, phases can be identified whose formation in the loading area roughens the material. In addition, temperature ranges can be identified, in which, for example, hot shaping should not occur, as phases are formed in them that strongly stiffen the material and thus lead to the formation of gaps in hot shaping . For good processability, especially in hot forming, such as, for example, hot rolling, forging, settlement, hot extrusion and similar processes, a sufficiently high temperature range must be available, in which these phases do not form. Description of properties
[00066] The alloy according to the invention, according to the task proposal, must have the following properties: • a wear resistance better than NiCr20TiAl • a corrosion resistance better than NiCr20TiAl • a thermal resistance / resistance to fluency comparable to NiCr20TiAl • good processability equivalent to NiCr20TiAl Wear resistance
[00067] The new material must have a better wear resistance than the reference alloy NCr20TiAl. In addition to this material, Stellite 6 was also tested for comparison. Stellite 6 is a cobalt based cast alloy, highly resistant to wear, with a tungsten carbide network, consisting of about 28% Cr, 1% Si, 2% Fe, 6% W, 1.2% C, remaining, Co, but which, due to its high carbide content needs to be melted directly into the desired shape. Due to its tungsten carbide network, Stellite 6 achieves a very high hardness of 438 HV30, which is very advantageous for wear. The "E" alloy according to the invention should be as close as possible to the volume loss of Stellite 6. The objective is, in particular, to reduce wear at high temperatures, between 600 and 800 ° C, which is the temperature range relevant, for example, for an application as a discharge valve. For this reason, the following criteria should apply, in particular, to the "E" alloys according to the invention: Average volume loss value ("E" alloy) <0.5 x average volume loss value (reference NiCr20TiAl ) at 600 ° C or 800 ° C (4a)
[00068] In the "low temperature range" of wear, the volume loss should not rise disproportionately. For this reason, the following criteria must additionally apply: Average volume loss value ("E" alloy) <1.3% x average volume loss value (NiCr20TiAl reference) at 25 ° C and 300 ° C (4b)
[00069] If in a series of measurements there is a volume loss of NiCr20TiAl for both an industrial load and a reference laboratory load, then the average value of these two loads is included in the inequalities (4a) or (4b). Thermal resistance / creep resistance
[00070] Table 3 shows the lower end of the dispersion band of the 0.2% elongation limit for NiCr20TiAl in the hardened state, the temperature between 500 and 800 ° C, Table 2 of the lower end of the dispersion band of the resistance to traction.
[00071] The 0.2% elongation limit of the alloy according to the invention must be set at 600 ° C at least within this value range or, at 800 ° C, not fall below that value range for no more than 50 MPa, to obtain sufficient strength. That is, the following values should be obtained, in particular: 600 ° C: elongation limit Rpo, 2> 650 MPa (5a) 800 ° C: elongation limit Rpo, 2> 390 MPa (5b)
[00072] For particularly high demands on thermal resistance, it is necessary that the alloys do not fall below this value range at 800 ° C, that is, 800 ° C: elongation limit Rpo, 2> 45 ° Mpa (5c)
[00073] Inequalities (5a) and (5b) are obtained, particularly, when the following relationship between Ti, Al, Fe, Co, Cr and C is satisfied: fh> 0 with (2a) fh = 6.49 + 3 , 88 Ti + 1.36 Al - 0.301 Fe + (0.759 - 0.0209 Co) Co • 0.428 Cr - 28.2 C (2) where Ti, Al, Fe, Co, Cr and C are the concentration of the elements corresponding in% by mass and fh is indicated in%.
[00074] Inequality (5c) can be additionally satisfied when it is worth: fh> 6 (2f) Corrosion resistance
[00075] The alloy according to the invention must have a corrosion resistance to air, similar to that of NiCr20TiAl. Processability
[00076] In nickel-chromium-iron-titanium-aluminum alloys, the thermal resistance or creep resistance is in the range of 500 ° C to 900 ° C in the addition of aluminum, titanium and / or niobium, which lead to the separation of phase 'or phase y'. When the hot shaping of this alloy is carried out within the scope of separation of these phases, then there is a risk of formation of fissures. The hot shaping should therefore occur, preferably above the temperature of solvus Tsy '(or Tsy' '). In order for a sufficient temperature range to be available for hot shaping, the solvus Tsy' (or Tsy '') temperature must be below 1020 ° C.
[00077] This is satisfied, particularly, when the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb is satisfied: fver <7 with (3a) fver = 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0.0109 Fe) Co + 40.67 Ti * Al + 33.28 Al2 - 13 , 6 Ti Al2 - 22.99 Ti - 92.7 Al + 2.94 Nb (3) with Cr, Mo, W, Fe, Co, Ti, Al and Nb being the concentration of the corresponding elements in% by mass and fver is indicated in%. Production Examples:
[00078] Tables 5a and 5b show the analysis of the molten loads on a laboratory scale, along with some industrially molten loads according to the state of the art (NiCr20TiAl), used for comparison. The loads according to the state of the art are characterized with a T, those according to the invention, with an E. The charges melted on a laboratory scale are characterized with an L, the charges melted industrially, with a G. The load 25021 is NiCr20TiAl, but fused as a laboratory charge, and serves as a reference.
[00079] The alloy blocks in Table 5a and b on a laboratory scale, vacuum-cast, were annealed between 1100 ° C and 1250 ° C for 0.1 to 70 hours and by means of hot rolling and other intermediate anneals between 1100 ° C e1250 ° C for 0.1 to 1 hour, hot rolled to a final thickness of 13 mm or 6 mm. The temperature conduction in the hot rolling was such that the plates were recrystallized. From these plates, the samples needed for measurements were produced.
[00080] The industrially cast comparative loads were cast by means of VIM and cast into blocks. These blocks were re-merged for ESU. These blocks were annealed between 1100 ° C and 1250 ° C for 0.1 min at 70 h, optionally under shielding gas, such as, for example, argon or oxygen, followed by cooling in air, in the moved annealing atmosphere or in the water bath and by means of hot rolling and other intermediate annealing between 1100 ° C and 1250 ° C for 0.1 to 20 hours, hot rolled in a final diameter between 17 to 40 mm. The temperature conduction in the hot rolling was such that the plates were recrystallized.
[00081] All alloy variants typically had a particle size of 2 to 52 μm (see Table 6).
[00082] After the samples were produced, they were hardened by annealing at 850 ° C for 4 hours / cooling in air, followed by annealing at 700 ° C for 16 hours / cooling in air.
[00083] Table 6 shows Vicker HV30 hardness, before and after hardening annealing. Hardness HV30, in the hardened state, is in all alloys, with the exception of load 250330, in the range of 366 to 416. Load 250330 has a slightly lower hardness of 346 HV30.
[00084] For the loads exemplified in Table 5a and 5b, the following properties are compared: • The wear resistance, with the help of a slip wear test • The corrosion resistance, with the help of an oxidation test • The resistance thermal / creep resistance, with the help of hot tensile tests • Processability with phase calculations Wear resistance
[00085] Wear tests were carried out at 25 ° C, 300 ° C, 600 ° C and 800 ° C in alloys according to the state of the art and in the various laboratory fusions. Most tests were repeated multiple times. Afterwards, mean values and standard deviations were determined.
[00086] Table 7 shows the mean values ± standard deviations of the measurements made. In the absence of a standard deviation, it is a single value. The composition of the charges is roughly described, for guidance, in Table 7, in the alloy column. Additionally, in the last line, the maximum values for the volume loss of the alloys according to the invention of the inequalities (4a) for 600 or 800 ° C and (4b) for 25 ° C and 300 ° C are registered.
[00087] Figure 1 shows the volume loss of the NiCr20TiAl pin load 320776, according to the state of the art, as a function of the test temperature, measured with 20 N, sliding path 1 mm, 20 Hz and with the module force measurement (a). The tests at 25 and 300 ° C were carried out for one hour and the tests at 600 and 800 ° C were carried out for 10 hours. The volume loss decreases strongly with temperature up to 600 ° C, ie wear resistance is noticeably improved at higher temperatures. In the context of high temperatures at 600 and 800 ° C, there is a comparatively less loss of volume and, therefore, less wear, which is based on the formation of a so-called "glaze" layer between pin and disk. This "glaze" layer consists of metal oxides and material from the pin and disc. The higher volume loss at 25 ° C and 300 ° C, despite the shorter time by factor 10, is based on the fact that the "glaze" layer cannot fully form at these temperatures. At 800 ° C, the volume loss rises slightly again, due to the higher oxidation.
[00088] Figure 2 shows the loss of volume of the NiCr20TiAl pin load 320776 according to the state of the art, as a function of the test temperature, measured with 20 N, sliding path 1 mm, 20 Hz and with the force measurement (n). For NiCr20TiAl load 320776, the same behavior is shown qualitatively as with the force measurement module (a): the volume loss decreases strongly with temperature, up to 600 ° C, with values at 600 and 800 ° C are even smaller than those measured with the force measurement module (a) Additionally, Figure 2 includes the values measured with Stellite 6. Stellite 6 shows at all temperatures, except for 300 ° C, an improved wear resistance (= less volume loss) than the comparative NiCr20TiAl alloy load 320776.
[00089] Volume losses at 600 and 800 ° C are very small, so that differences between different alloys can no longer be reliably measured. For this reason, a test was also carried out at 800 ° C, with 20 N for 2 hours + 100N for 5 hours, sliding path 1 mm, 20 Hz, with the force measurement module (n), to generate wear slightly higher also in the context of high temperature. The results are shown in Figure 3, together with the volume losses measured with 20 N, sliding path 1 mm, 20 Hz and force measurement module (n), at different temperatures. The volume loss in the context of high wear temperature has thus been markedly increased.
[00090] The comparison of the different alloys was carried out at different temperatures. In Figures 4 to 8, the laboratory loads are characterized by an L. The most important change in relation to the industrial load 320776 is indicated in the figures, in addition to the laboratory load number with element and rounded value. The exact values are found in Tables 5a and 5b. Rounded values are used in the text.
[00091] Figure 4 shows the loss of pin volume for different laboratory loads compared to NiCr20TiAl load 320776 and Stellite 6, at 25 ° C, after 1 h, measured with 20 N, sliding path 1 mm, 20 Hz , with force measurement module (a) and (n). The values with the force measurement module (n) were systematically lower than those with the force measurement module (a). Taking this into account, it can be seen that NiCr20TiAl, both as laboratory load 250212 and as industrial load 320776, had a similar volume loss in terms of measurement accuracy. Laboratory loads can therefore be compared directly with industrial loads for wear measurements. The 250325 load, with about 6.5% Fe, showed at 25 ° C a volume loss less than the maximum value of (4b) for the two force measurement modules (see Table 7). The volume loss of charge 250206, with 11% Fe, tended to fall within the upper dispersion range of charge 320776, but the mean value was also less than the maximum value of (4a). The load 250327, with 29% Fe, showed in the measurements with the force measurement module (n) a slightly increased volume loss, but the average value here was also less than the maximum value of (4b) for both force measurement modules. The laboratory charges containing Co showed, on the other hand, a volume loss that tended to be smaller than in the charge 250209 (9.8% Co), with the force measurement module (n), with 1.04 +/- 0.01 mm3, has just left the load dispersion range 320776. In load 250229 (30% Co), with 0.79 +/- 0.06 mm3, a clear reduction in volume loss, which afterwards, in the load 250330, by the addition of 10% Fe, with 0.93 + / 0.02 mm3, increased again, slightly. The volume loss of the 3 charges according to the invention, which contain Co, 250209. 250329 and 250330 was clearly below the maximum value of the criterion (4b) for the two force measurement modules, so that the inequality ( 4a) was satisfied. The increase in Cr content in load 250326 to 30% compared to 20% in load 320776 generated an increase in volume wear to 1.41 +/- 0.18 mm3, but it was also below the maximum value of (4a ).
[00092] Figure 5 shows the pin volume loss for alloys with different carbon contents, compared to NiCr20TiAl, load 320 776, measured at 25 ° C, with 20 N, sliding path 1 mm, 20 Hz, with force measurement module (a), after 10 hours. There was no change in volume loss compared to load 320776, neither by a reduction in carbon content to 0.01% in load 250211, nor by an increase to 0.211% in load 250214.
[00093] Figure 6 shows the loss of pin volume for several alloys, compared to NiCr20TiAl, load 320776, measured at 300 ° C, with 20 N, sliding path 1 mm, 20 Hz, after 1 hour, with the force measurement modules (a) and (n). The values with the force measurement module (n) are systematically lower than those with the force measurement module (a). Taking this into account, below, then it can be seen that at 300 ° C, Stellite 6 was worse than the load 320776. In the case of laboratory fusions containing Co, 250329 and 250330, there was no reduction in the wear volume, such as at room temperature, but it was within the scope of the NiCr20TiAl volume, load 320776 and, therefore, did not show any increase, as in the Stellite 6. The volume loss of all 3 loads according to the invention containing Co, 250209, 250329 and 250330, it was clearly below the maximum value of the criterion (4b). Contrary to the behavior at room temperature, laboratory fusions containing Fe, 250206 and 250327 showed a smaller volume loss with increasing Fe content, which, therefore, was below the maximum value (4b). The laboratory load 250326 according to the invention, with a Cr content of 30%, had a volume loss under NiCr20TiAl, load 320776.
[00094] Figure 7 shows the loss of pin volume for several alloys, compared to NiCr20TiAl, load 320776, measured at 600 ° C, with 20 N, sliding path 1 mm, 20 Hz and with force measurement module (a) and (n), after 10 hours. The values with the force measurement module (n) were systematically lower than those with the force measurement module (a). It can be seen that also in the context of high wear temperatures, the reference laboratory load 250212 for NiCr20TiAl, with 0.066 +/- 0.02 mm3, a comparable volume loss, as did the industrial load 320776, with 0.053+ / -0.0028 mm3. Laboratory loads can therefore be compared directly with industrial loads, in terms of wear measurements, also within this temperature range. Stellite 6 shows a smaller volume loss by factor 3, 0.009 +/- 0.002 mm3 (force measurement module (n)). Furthermore, it showed that neither by a reduction in the carbon content to 0.001% in load 250211, but also by an increase to 0.211% in load 250214, a modification of the volume loss was obtained, in comparison with load 320778 and 250212 (force measurement module (a)). Also the addition of 1.4% manganese in the 250208 load or 4.6% tungsten in the 250210 load did not lead to any significant change in volume loss, compared to the 320776 and 250212 load. The 250206 load with 11% Fe, with 0.025 +/- 0.003 mm3, showed a clear reduction in volume loss, compared to the load 320776 and 250212 to 0.025 +/- 0.003 mm3, which is less than the maximum value of (4a). In the load 250227, with 29% Fe, the volume loss, with 0.05 mm3, was comparable with that of the load 320776 and 250212. Also in the laboratory load 250209, with 9.8 Cr, it was smaller than than the maximum value of (4a). 9.8% Co, the loss of volume with 0.0642 mm3 was comparable to that of the load 250330 and 250212. In laboratory loads 250329, with 30% Co, and 250330, with 29% Co and 10% de Fe, the volume loss, with 0.020 or 0.029 mm3 was clearly less than that of the load 320776 and 250212, which is less than that of the maximum value of (4a). For a similarly low value of 0.026 mm3, the volume loss of the charge 250326 according to the invention, with a Cr content increased to 30%, was less than the maximum value of (4a).
[00095] Figure 8 shows the loss of pin volume for the different alloys, compared to NiCr20TiAl, load 320776, at 800 ° C, with 20 N for 2 hours, followed by 100 N for 3 hours, all along the way sliding speed of 1 mm, 20 Hz, measured with the force measurement module (n). Also at 800 ° C, it was found that in the context of high wear temperatures, the reference laboratory load 250212 for NiCr20TiAl, with 0.292 +/- 0.016 mm3, had a comparable volume loss, as did the industrial load 320776, with 0.331 +/- 0.081 mm3. The laboratory loads could therefore be compared directly with industrial loads, in terms of wear measurements, even at 800 ° C. The load 250325, with 6.5% iron, showed with 0.136 +/- 0.025 mm3, a clear reduction in volume loss, compared to the load 320776 and 250212, below the maximum value of 0.156 mm3 of (4a). In load 250206, with 11% iron, it was shown with 0.057 +/- 0.007 mm3, an additional reduction in volume loss, in comparison with load 320776. In load 250327, with 29% Fe, the volume loss was 0.043 +/- 0.02 mm3. Both times, these are values that were clearly below the maximum value of 0.156 mm3 of (4a). Also in laboratory load 250209, with 9.8% Co, the volume loss of 0.144 +/- 0.012 mm3, decreased to a value similar to that of laboratory load 250325, with 6.5% iron - below the maximum value of 0.156 mm3, of inequality (4a). In laboratory load 250329, with 30% Co, another reduction in volume loss was shown to 0.061 +/- 0.005 mm3 ,, which is clearly below the maximum value of 0.156 mm3 of the inequality (4a). In laboratory load 250330, with 29% Co and 10% Fe, the volume loss fell again by the addition of Fe, with 0.021 +/- 0.001 mm3.
[00096] To a similarly low value of 0.042 +/- 0.011 mm3, such as that of the charge 250206, with 11% iron, the volume loss of the charge 250326 was reduced by a Cr content increased to 30%.
[00097] Particularly, at values measured at 800 ° C, it was shown that the loss of pin volume in the wear test could be strongly reduced in the alloys according to the invention by a Co content between> 3 and 40%, so that in one of the two temperatures, 600 or 800 ° C, it was less / equal to 50% of the volume loss of NiCr20TiAl (4a). The alloys according to the invention with a Co content of> 3 to 40%, also at 25 ° C and 300 ° C, satisfy the inequalities (4b).
[00098] In laboratory load 250209 according to the invention, with 10% Co, the volume loss at 800 ° C dropped to 0.144 +/- 0.012 mm3, below the maximum value of (4a). At 25, 300 and 600 ° C, there was no increase in wear. In the laboratory load 250329 according to the invention, with 30% Co, the volume loss at 800 ° C fell again, clearly, to 0.061 +/- 0.005 mm3, below the maximum value of (4a). The same was shown at 600 ° C, with a reduction to 0.020 mm3, below the maximum value of (4a). At 25 ° C, the laboratory load 250329 according to the invention showed with 30% Co, a reduction to 0.93 +/- 0.02 mm3, with the force measurement module (n). Even at 300 ° C, this laboratory load showed 0.244 mm3, a wear similar to the reference load 320776 and 250212, totally unlike the alloy in the cobalt base Satellite 6, which at this temperature showed a volume loss clearly more higher than the reference load 3207776 and 250212 showed. In the laboratory load according to the invention 250330, by addition of 10% iron, in addition to 29% Co, an additional wear reduction at 800 ° C could be obtained , to 0.21 +/- 0.001 mm3. Thus, an optional iron content, between 0 and 20%, is advantageous.
[00099] Also the load 250336, with 30% chromium, showed at 800 ° C a reduction in volume loss to 0.042 +/- 0.011 and also at 600 ° C to 0.026 mm3, both below the respective maximum value of (4a ). At 300 ° C, the volume loss, at 0.2588 mm3, was also below the maximum value of (4a), as well as at 25 ° C, at 1.41 +/- 0.18 mm3 (measuring module strength (n)), so that chromium contents between 18 and 31% are advantageous, particularly for wear at high temperatures.
[000100] Figure 9 shows the pin volume loss for the various alloys in Table 7, at 800 ° C, with 20 N for 2 hours, followed by 100 N for 3 hours, all measured with the slip path of 1 mm, 20 Hz, with force measurement module (n), together with the sum Cr + Fe + Co of formula (1) for very good wear resistance. It can be seen that the loss of volume at 800 ° C was all the less when the greater the sum of Cr + Fe + Co and inversely. The formula Cr + Fe + Co> 26% is, therefore, a criterion for very good wear resistance in the alloys according to the invention.
[000101] NiCr20TiAl alloys according to the state of the art, loads 320776 and 250212, had a sum of Cr + Fe + Co of 20.3 or 20.2%, the two less than 26%, and meet the criteria (4a) and (4b) for very good wear resistance, but in particular they do not meet the criteria (4a) for wear resistance at high temperatures. Also the loads 250211, 250214, 250208 and 250210 do not meet the criteria (4a) for good resistance to wear at high temperatures and had a sum of Cr + Fe + Co of 20.4%, 20.2%, 20.3 % or 20.3%, all less than 26%. The loads 250325, 250206, 250327, 250209, 250329, 250330 and 250326, with additions of Fe and Co or an increased Cr content, particularly the load 250326 according to the invention, meet the criteria (4a), throughout case, to 800 ° C, partly even further, to 600 ° C, and had a sum of Cr + Fe + Co, of 26.4%, 30.5%, 48.6%, 29.6%, 50.0%, 59.3% or 30.3%, all greater than 25. Thus, they satisfy equation (1), for good wear resistance. Thermal resistance / creep resistance
[000102] Table 8 shows the elongation limit Rp0.2 and the tensile strength Rm for room temperature (RT), for 600 ° C and 800 ° C. In addition, the measured particle sizes and values for fh are entered. Additionally, the minimum values of inequalities (5a) and (5b) are inscribed on the last line.
[000103] Figure 10 shows the elongation limit Rp0.2 and the tensile strength Rm to 600 ° C, Figure 11, to 800 ° C. The cast loads 321863, 321426 and 315828, for the elongation limit Rp0.2, at 600 ° C, values between 841 and 885 Mpa and at 800 ° C, values between 472 and 881 Mpa. The reference laboratory load 250212, with a similar analysis, as that of industrial loads, had a slightly higher aluminum content, of 1.75%, which at 600 ° C led to a slightly elongation limit Rp0.2 higher, of 866 Mpa and at 800 ° C, of 491 Mpa.
[000104] At 600 ° C, as shown in Table 8, the elongation limits Rp0.2 of all laboratory loads (L), therefore, also of the loads according to the invention (E), and all loads industrial (G) greater than 650 Mpa, therefore criterion (5a) was satisfied.
[000105] At 800 ° C, as shown in Table 8, the elongation limits Rp0.2 of all laboratory loads (L), therefore, also of the load (E) according to the invention, and all loads (G), were greater than 390Mpa, therefore, inequality (5b) was satisfied.
[000106] Observation of laboratory load 250212 (reference, similar to industrial loads, without addition of Co) or also of industrial loads and loads according to the invention 250209 of (9.8% of Co) 25329 (9, 8% Co) showed that a 9.8% Co content increased the elongation limit Rp0.2 in the tensile test at 800 ° C to 526 Mpa, an additional increase to 30% Co led again to a slight reduction to 489 Mpa (see also Figure 11). In this case, not only criterion (b) is met, but also criterion (5c) for a particularly high thermal resistance / creep resistance. An optional alloy content of> 3% to 40% Co in the alloy according to the invention is advantageous to obtain an elongation limit Rp0.2 at 800 ° C of greater than 390 Mpa (5b), or even greater than 450 Mpa (5c).
[000107] A certain proportion of iron may be advantageous in the alloy for reasons of cost. The load 250327 with 29% Fe satisfied the inequality (5b) only to a limited extent, as, as shown by the observation of laboratory load 250212 (reference, similar to industrial loads, Fe less than 3%) or also industrial loads and the loads according to the invention 250325 (6.5% Fe) 250206 (11% Fe) and 250 327 (29% Fe), an increasing Fe content in the alloy, decreases the Rp0 elongation limit. 2 in the tensile test (see also Figure 11). For this reason, an optional alloy content of 20% Fe can be seen as an upper limit for the alloy according to the invention.
[000108] Lab load 250326 showed that at an addition of 30% Cr, the elongation limit Rp0.2 decreased in the tensile test at 800 ° C to 415 MPa, which was still significantly above the minimum value of 390 Mpa. For this reason, an alloy content of 31% Cr should be seen as an upper limit for the alloy according to the invention.
[000109] Figure 12 shows the elongation limit Rp0.2 and fh, calculated according to formula (2) for good thermal resistance or creep resistance for the various alloys in Table 8, at 800 ° C. It can be clearly seen that fh rises and falls within the range of measurement accuracy, such as the elongation limit, at 800 ° C. Thus, fh describes the Rpo.2 elongation limit at 800 ° C. An fh> 0 is necessary to obtain sufficient thermal resistance or resistance to creep, as seen, particularly, in load 250327, with Rp0.2 = 391 Mpa, a value that is just over 390 Mpa. This load also has fh = 0.23%, a value that is just slightly above the minimum value of 0%. The alloys according to the invention 250209, 250329 and 250330 according to the invention have an fh> 6 (2f) and at the same time satisfy the inequality (5c). Corrosion resistance:
[000110] Table 9 shows the specific mass modifications according to an oxidation test at 800 ° C in air, after 6 cycles of 96 h, therefore, in total, 576 h. Table 9 shows the modification of the specific gross mass, the modification of the specific liquid mass and the modification of the specific mass of the chipped oxides, after 576 h. The exemplified loads of the alloys according to the state of the art NiCr20TiAl, loads 321426 and 250212 showed a modification of specific gross mass of 9.69 or 10.84 g / m2 and a modification of specific net mass of 7.81 or 10, 54 g / m2. Load 321426 showed negligible splinters. The loads according to the invention 25209 (Co 9.8%) and 250329 (Co 30%) had a modification of gross specific mass of 10.0 or 9.91 g / m2 and a modification of specific net mass of 9.81 or 9.71 g / m2 which are below the scope of the NiCr20TiAl reference alloys and, as required, were no worse than the same. In the same way the load according to the invention behaved 250330 (29% Co, 10% Fe), with a modification of specific gross mass of 9.32 g / m2 and a modification of specific liquid mass of 8.98 g / m2. A content of Co> 3 to 40%, therefore, does not negatively influence resistance to oxidation. Loads containing iron 250325 (Fe 6.5%), 250206 (Fe 11%) and 250327 (Fe 29%) also showed a change in specific gross mass from 9.26 to 10.92 g / m2 and a change in mass specific net of 9.05 to 10.61 g / m2, which were within the scope of NiCr20TiAl reference alloys and, as required, were also not worse. Therefore, an Fe content of up to 30% does not influence oxidation resistance. The 250326 filler, with an increased chromium content of 30%, had a modification of 6.74 g / m2 gross mass and a modification of 6.84 g / m2 net mass, which are below the scope of the reference alloys NiCr20TiAl. A Cr content of 30% improved the oxidation resistance.
[000111] All alloys according to Table 5b contain Zr, which as a reactive element contributes to the improvement of corrosion resistance. Optionally, other reactive elements can then be added, such as Y, La, Ce, mixed cerium metal, Hf, which improve efficiency in a similar way. Processability
[000112] Figure 13 shows the phase diagram calculated with JmatPro of the NiCr20TiAl load 321426 according to the state of the art. Below the 959 ° C Tsus 'solvus temperature, the y' phase is formed, with, for example, a proportion of 26%, at 600 ° C. Then the phase diagram shows the formation of Ni2M (M = Cr) below 558 ° C, with proportions of up to 64%. This phase, however, is not observed in the use of this material with the combinations that occur in the practice of use temperature and time and, for this reason, it does not need to be taken into account. In addition, Figure 13 also shows the scope of existence of various carbides and nitrides, but that do not prevent hot shaping in these concentrations. Hot shaping can only occur above the Tsy 'solvus temperature, which, in order for a sufficient temperature range to be available below the solvus temperature, 1310 ° C for hot shaping, must be less than / equal to 1020 ° Ç.
[000113] For the alloys in Table 5a and 5b, for this reason, the phase diagrams were calculated, and the Tsy 'solvus temperature was entered in Table 5a. For the compositions in Tables 5a and 5b, the fver value was also calculated according to formula (3). Fver is higher the higher the temperature of Tsy ’solvus. All alloys in Table 5a, including the alloys according to the invention, have a calculated solvus Tsy 'temperature less than / equal to 1020 ° C and meet criterion (3a): fver <7%. Inequality fver <7% (3a) is, therefore, a good criterion for obtaining a sufficiently large hot shaping scope and, therefore, good processability of the alloy.
[000114] The claimed limits for the alloys according to the invention "E" can be justified individually, as follows:
[000115] Cr contents too small mean that the concentration of Cr in the use of the alloy in a corrosive atmosphere quickly falls below the critical limit, so that a closed chromium oxide layer can no longer form. For this reason, 18% is the lower limit for chromium. Too high Cr levels increase the temperature of Tsy 'solvus in such a way that the processability deteriorates markedly. Therefore, 31% should be seen as an upper limit.
[000116] Titanium increases the resistance to high temperatures, at temperatures up to 900 ° C, by promoting the formation of the y 'phase. To obtain sufficient strength, at least 1% is required. Too high titanium contents increase the temperature of Tsy 'solvus in such a way that the processability deteriorates sharply. Therefore, 3.0% should be seen as an upper limit.
[000117] Aluminum increases resistance to high temperatures, at temperatures up to 900 ° C, by promoting the formation of the y 'phase. To obtain sufficient strength, at least 0.6% is required. Too high aluminum contents increase the temperature of Tsy 'solvus in such a way that the processability deteriorates sharply. Therefore, 2.0% should be seen as an upper limit.
[000118] Cobalt increases, particularly, in the context of high temperatures, the thermal resistance / creep resistance. To obtain sufficient wear resistance, at least> 3.0% is required. Too high cobalt levels increase costs too much. For this reason, 40% should be seen as an upper limit.
[000119] Carbon improves creep resistance. A minimum content of 0.005% C is required for good creep resistance. Carbon is limited to a maximum of 0.10%, since this element, from that content, reduces the processability, due to the excessive formation of primary carbides.
[000120] A minimum content of 0.0005% N is required for reasons of cost. N is limited to a maximum of 0.050%, since this element, due to the formation of thick carbon nitrides, reduces the processability.
[000121] The phosphorus content must be less / equal to 0.030%, since this element of surface activity impairs the resistance to oxidation. Too little phosphorus content increases costs. The phosphorus content is therefore> 0.0005%.
[000122] Sulfur contents should be adjusted to the lowest possible level, since this element with surface activity impairs oxidation resistance and processability. Therefore, a maximum of 0.010% of S.
[000123] The oxygen content needs to be less than / equal to 0.020%, to guarantee the processability of the alloy.
[000124] Too high silicon content impairs processability. The Si content is therefore limited to 0.70%.
[000125] Manganese is limited to 2.0%, as this element reduces resistance to oxidation.
[000126] Already very small contents of Mg and / or Ca improve the processability by sulfur bonding, avoiding the occurrence of low fusion NiS eutectic. At levels that are too high, Ni-Mg phases or Ni-Ca intermetallic phases may occur, which, in turn, clearly deteriorate the processability. The Mg content or the Ca content is therefore limited, in each case, to a maximum of 0.05%.
[000127] Molybdenum is limited to a maximum of 2.0%, as this element reduces resistance to oxidation.
[000128] Tungsten is limited to a maximum of 2.0%, as this element also reduces resistance to oxidation and possible carbon levels in forged alloys has no positive, measurable effect on wear resistance.
[000129] Niobium increases resistance to high temperatures. Higher levels increase costs sharply. The upper limit is therefore set at 0.5%.
[000130] Copper is limited to a maximum of 0.5%, as this element reduces resistance to oxidation.
[000131] Vanadium is limited to a maximum of 0.5, as this element reduces resistance to oxidation.
[000132] Iron increases, particularly in the context of high temperatures, the resistance to wear. It also reduces costs. Therefore, it can optionally be present between 0 and 20% in the alloy. Too high iron contents reduce the elongation limit too strongly, particularly at 800 ° C. Therefore, 20% should be seen as an upper limit.
[000133] If necessary, the alloy can also contain Zr, to improve resistance to high temperatures and resistance to oxidation. The upper limit is set, for cost reasons, at 0.20% Zr, since Zr is a rare element.
[000134] If necessary, boron can be added to the alloy, as boron improves creep resistance. Therefore, at least a content of 0.0001% must be present. At the same time, this element with surface activity deteriorates the resistance to oxidation. Therefore, a maximum of 0.008% of boron is defined.
[000135] Nickel stabilizes the austenitic matrix and is necessary for the formation of the y 'phase, which contributes to thermal resistance / creep resistance. At a nickel content below 35%, the thermal resistance / creep resistance is reduced too strongly, which is why 35% is the inferred limit.
[000136] The following relationship between Cr. Fe and Co need to be satisfied, so that, as explained in the examples, there is sufficient wear resistance Cr + Fe + Co> 25% (1) with Cr, Fe and Co being the concentration of said elements in% in pasta.
[000137] In addition, the following relationship must be satisfied, so that there is sufficient resistance at high temperatures: fh> 0 with (2a) fh = 6.49 + 3.88 Ti + 1.36 Al - 0.301 Fe + ( 0.759 - 0.0209 Co) Co - 0.428 Cr - 28.2 C, (2) where Ti, Al, Fe, Co, Cr and C are the concentration of the corresponding elements in% by mass and fh is indicated in%. The limits for fh were justified in detail in the preceding text.
[000138] If necessary, the resistance to oxidation can be further improved with additions of elements containing oxygen, such as yttrium, lanthanum, cerium, hafnium. This is done by the fact that they are included in the oxide layer and there block the diffusion paths of oxygen at the boundaries of the particles.
[000139] The upper limit of yttrium is determined for reasons of costs by 0.20%, since yttrium is a rare element.
[000140] The upper limit of lanthanum is determined for reasons of costs at 0.20%, since lanthanum is a rare element.
[000141] The upper limit of cerium is determined for reasons of costs at 0.20%, since cerium is a rare element.
[000142] Instead of Ce and / or La, mixed metal of cerium can also be used. The upper limit for mixed cerium metal is set at 0.20% for cost reasons.
[000143] The upper limit of hafnium is determined for reasons of costs at 0.20%, since hafnium is a rare element.
[000144] If necessary, the alloy may also contain tantalum, since tantalum also increases resistance to high temperatures by promoting the formation of y-phases. Higher levels increase costs strongly, since tantalum is a rare element. The upper limit is therefore determined at 0.60%.
[000145] Pb is limited to a maximum of 0.0002%, since this element reduces resistance to oxidation and resistance to high temperatures. The same goes for Zn and Sn.
[000146] In addition, the following relationship between Cr. Mo, W, Fe, Co, Ti, Al and Nb must be satisfied, so that there is sufficient processability: fver <7 with: (3a) fver = 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0.0109 Fe) Co + 40.67 Ti * Al + 33.28 Al2 - 13.6 Ti Al2 - 22, 99 Ti - 92.7 Al + 2.94 Nb (3) [1] where Cr, Mo, W, Fe, Co, Ti, Al and Nb are the concentration of the corresponding elements in mass% and fver is indicated in %. The upper limits for fh were sufficiently justified in the preceding text, Table 1: Composition of nickel alloys mentioned in DIN EN 10090 for discharge valves. All data in mass%
Table 2: Guideline values for high temperature tensile strength of nickel alloys mentioned in DIN EN 10090 for discharge valves (+ AT annealed in solution: 1000 to 1080 ° C cooling in air or water, + P hardened by separation: 890 to 710/16 h air; 1). The values shown here are located in the vicinity of the lower dispersion band)
Table 3: Guidance values for the 0.2% elongation limit at high temperatures of the nickel alloys mentioned in DIN EN 10090 for discharge valves (+ annealed in solution: 1000 to 1080 ° C cooling in air or water , + P hardened by separation: 890 to 710/16 h air 1). The values shown here are located in the vicinity of the lower dispersion band)
Table 4: Guideline values for creep resistance after 1000 hours at high temperatures of the nickel alloys mentioned in DIN EN 10090 for discharge valves (+ AT annealed in solution: 1000 to 1080 ° C cooling in air or water, + P hardened by separation 890 bis 710/16 h air; 1). Average values of the dispersion scopes detected
Table 5a: Composition of industrial and laboratory fillers, part 1. All concentration data in mass% (T: alloy according to the state of the art, E: alloy according to the invention, L: cast on a laboratory scale , G: industrially cast)
Table 5b: Composition of industrial and laboratory loads, Part 2. All data in mass%. P = 0.0002%, Sn <0.01%, If <0.0003% Te <0.0001%, Bi <0.00003% Sb <0.0005% Ag <0.0001% (T: alloy of according to the state of the art, E: alloy according to the invention L: cast on laboratory scale, G: cast on industrial scale).
Table 6: Result of particle size determination and NV30 hardness measurement at room temperature (RT) before (HV30_r) and after (HV30_h) hardening annealing (850 ° C for 4 h / cooling in air, followed by a annealing at 700 ° C for 16 h / cooling in air); KG = particle size (T: alloy according to the state of the art, E: alloy according to the invention L: molten on a laboratory scale, G: melted industrially).
Table 7: Pin wear volume in mm3 at a load of 20 N, with a slip path of one mm, a frequency of 20 Hz and an air humidity of around 45% of industrial and laboratory loads (alloy of according to the state of the art, E: alloy according to the invention L: cast on laboratory scale, G: cast on industrial scale) 1. Measuring system (n) 2. Measuring system (2). Mean values ± standard deviation are indicated. With the standard deviation missing, it is a single value.

Table 8: Results of tensile tests at room temperature (RT), 600 ° C and 800 ° C. The transformation speed was Rp0.2 8.33 10-5 1 / s (0.5% / min) and Rm 8.33 10-4 1 / s (5% / min); KG = particle size. (T: alloy according to the state of the art, E: alloy according to the invention, L: cast on laboratory scale G: industrial cast) *) Defective measurement.
Table 9: Results of oxidation tests at 800 ° C in air after 576 h (T: alloy according to the state of the art, E: alloy according to the invention, L: cast on laboratory scale G: cast on industrial basis)
List of reference signals Figure 1: Loss of volume of the NiCr20TiAl pin load 320776 according to the state of the art as a function of the test temperature, measured with 20 N, sliding path 1 mm, 20 Hz and with the measuring module of strength (a). Tests at 25 and 300 ° C were performed for 1 hour and tests at 600 and 800 ° C were performed for 10 hours. Figure 2: Loss of volume of the NiCr20TiAl pin load 320776 according to the state of the art and the cast alloy Stellite 6 as a function of the test temperature, measured with 20 N, sliding path 1 mm, 20 Hz and with the force measurement (n). Tests at 25 and 300 ° C were performed for 1 hour and tests at 600 and 800 ° C were performed for 10 hours. Figure 3: Loss of volume of the NiCr20TiAl pin load 320776 according to the state of the art as a function of the test temperature, measured with 20 N, sliding path 1 mm, 20 Hz and with the force measurement module (n) . Tests at 25 and 300 ° C were performed for 1 hour and tests at 600 and 800 ° C were performed for 10 hours. Additionally, a test was carried out at 800 ° C, with 20 N, for 2 hours + 100 N, for 5 hours. Figure 4: Loss of pin volume for various alloys in Table 7, measured at 25 ° C, with 20 N, sliding path 1 mm, 20 Hz, after 1 hour, with force measurement module (a) and ( n). Figure 5: Loss of pin volume for alloys with different carbon content in Table 7, compared to NiCr20TiAl Load 320776, measured at 25 ° C, with 20 N, sliding path 1 mm, 20 Hz, with measurement module strength (a), after 10 hours. Figure 6: Loss of pin volume for several alloys in Table 7, measured at 300 ° C, with 20 N, sliding path 1 mm, 20 Hz, with force measurement module (a) and (n), after 1 hour. Figure 7: Loss of pin volume for various alloys in Table 7, measured at 600 ° C, with 20 N, sliding path 1 mm, 20 Hz, after 10 hours, with force measurement module (a) and ( n). Figure 8: Loss of pin volume for several alloys in Table 7, measured at 800 ° C, with 20 N, for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz slip path, and with force measurement module (n). Figure 9: Loss of pin volume for several alloys in Table 7, measured at 800 ° C, with 20 N, for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz slip path, and with force measurement module (n), together with the sum Cr + Fe + Co of the formula (1). Figure 10: Elongation limit Rp0.2 and tensile strength Rm for the alloys in Table 8, at 600 ° C (L: cast in laboratory scale, G; industrial cast). Figure 11: Elongation limit Rp0.2 and tensile strength Rm for the alloys in Table 8, at 800 ° C (L: cast on laboratory scale, G; cast on industrial basis). Figure 12: Elongation limit Rp0.2 and fh, calculated according to formula 2 for the alloys in Table 8, at 800 ° C (L: cast on laboratory scale, G; cast on industrial basis). Figure 13: Proportions in quantity of the phases in thermodynamic equilibrium, depending on the temperature of NiCr20TiAl in the example of load 321426 according to the state of the art in Table 5a and 5b.

权利要求:
Claims (14)
[0001]
1. Forging nickel-chromium-cobalt-titanium-aluminum alloy, which comprises very good wear resistance, with very good creep resistance, good corrosion resistance at high temperatures and good processability. of, said alloy being characterized by the fact that it comprises (in mass%):> 18 to 26% by weight of chromium, 1.5 to 3.0% of titanium, 0.6 to 2.0% aluminum,> 15 to 35% cobalt, 0.005 to 0.10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, max. 0.010% sulfur, max. 0.020% oxygen, max. 0.70% silicon, max. 2.0% manganese, max. 0.05% magnesium, max. 0.05% calcium, max. 0.5% molybdenum, max. 0.5% tungsten, max. 0.2% niobium, max. 0.5% copper, max. 0.5% vanadium, if necessary, 0 to 20% Fe, if necessary, 0 to 0.20% Zr, if necessary, 0.0001 to 0.008% boron, the following elements may still be optional - onally contained in the alloy: Y 0 - 0.20% and / or La 0 - 0.20% and / or Ce 0 - 0.20% and / or Mixed metal of cerium 0 - 0.20% and / or Hf 0 - 0.20% and / or Ta 0 - 0.60% the remainder being nickel and the usual impurities resulting from the process, proportions being adjusted from max. 0.002% Pb, max. 0.002% Zn, max; 0.002% of Sn, with a nickel content greater than 35%, and the following ratios must be satisfied: Cr + Fe + Co> 25% (1) to obtain good wear resistance, and fh> 0 with (2a) fh = 6.49 +3.88 Ti + 1.36 Al - 0.301 Fe + (0.759 - 0.0209 Co) Co - 0.428 Cr - 28.2 C, (2) so that a resistance is obtained sufficient at high temperatures, where T, Al, Fe, Co, Cr and C are the concentration of the corresponding elements in% by mass, and fh is indicated in%.
[0002]
2. Alloy according to claim 1, characterized by the fact that it comprises an aluminum content between 0.9 and 2.0%.
[0003]
3. Alloy according to claim 1, characterized by the fact that it comprises a carbon content between 0.01 and 0.10%.
[0004]
Alloy according to any one of claims 1 to 3, characterized by the fact that it optionally comprises an iron content between> 0 and 15.0%.
[0005]
Alloy according to any one of claims 1 to 4, characterized by the fact that it optionally comprises a boron content between 0.0005 and 0.006%.
[0006]
6. An alloy according to any one of claims 1 to 5, characterized by the fact that it comprises a nickel content greater than 40%.
[0007]
Alloy according to any one of claims 1 to 6, characterized by the fact that it comprises a nickel content greater than 45%.
[0008]
An alloy according to any one of claims 1 to 7, characterized by the fact that it comprises a nickel content greater than 50%.
[0009]
9. Alloy according to any one of claims 1 to 8, characterized by the fact that it presents: Cr + Fe + Co> 26% (1a) where Cr, Fe and Co are the concentration of the corresponding elements in mass% .
[0010]
10. Alloy according to any one of claims 1 to 9, characterized by the fact that it presents: fh> 1 with (2b) fh = 6.49 + 3.88 Ti + 1.36 Al - 0.301 Fe + (0.759 - 0.0209 Co) Co - 0.428 Cr - 28.2 C (2) where Cr, Fe, Co, and C are the concentration of the corresponding elements in mass%, and fh is indicated in%.
[0011]
11. Alloy according to any one of claims 1 to 10, characterized by the fact that optionally the following relations must be satisfied between Cr, Mo, W, Fe, Co, Ti, Al and Nb, so that sufficient processability is obtained: fver = <7 with (3a) fver = 32.77 + 0.5932 Cr + 0.3642 Mo + 0.513 W + (0.3123 - 0.0076 Fe) Fe + (0.3351 - 0.003745 Co - 0.0109 Fe) Co + 40.67 Ti * Al + 33.28 Al2 - 13.6 Ti Al2 - 22.99 Ti - 92.7 Al + 2.94 Nb (3) with Cr, Mo, W , Fe, Co, Ti, Al and Nb are the concentration of the corresponding elements in% by mass, and fver is indicated in%.
[0012]
12. Use of the alloy, as defined in any one of claims 1 to 11, characterized by the fact that it is like tape, plate, wire, bar, welded pipe in longitudinal seam and seamless pipe.
[0013]
13. Use of the alloy, as defined in any of claims 1 to 12, characterized by the fact that it is for valves, particularly discharge valves for internal combustion engines.
[0014]
14. Use of the alloy, as defined in any of claims 1 to 12, characterized by the fact that it is like gas turbine components, like fixing pins, in springs, in turbochargers.

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同族专利:

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KR20160137511A|2016-11-30|

WO2015117583A1|2015-08-13|

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DE102014001330A1|2015-08-06|

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法律状态:
2018-04-24| B25A| Requested transfer of rights approved|Owner name: VDM METALS INTERNATIONAL GMBH (DE) |

2019-08-06| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-09-08| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

2021-01-05| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 12/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

DE102014001330.8A|DE102014001330B4|2014-02-04|2014-02-04|Curing nickel-chromium-cobalt-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability|

DE102014001330.8|2014-02-04|

PCT/DE2015/000007|WO2015117583A1|2014-02-04|2015-01-12|Hardening nickel-chromium-cobalt-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability|

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