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    • 专利摘要:
    NICKEL-CHROME-IRON-TITANIUM-ALUMINUM ALLOY ALLOY WITH GOOD WEAR RESISTANCE, FLUENCE RESISTANCE, CORROSION RESISTANCE AND PROCESSABILITY. The present invention relates to a forged nickel-chromium-iron-titanium-aluminum alloy of hardening, at the same time, with good creep resistance, good resistance to corrosion at high temperature and good processability with (in mass%) (greater than) 18 to 31% chromium, 1.0 to 3.0% titanium, 0.6 to 2.0% aluminum, (greater than) 3.0 to 40% iron, 0.005 to 0, 10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, maximum 0.010% sulfur, maximum 0.020% oxygen, maximum 0.70% silicon, maximum 2 0% manganese, maximum 0.05% magnesium, maximum 0.05% calcium, maximum 2.0% molybdenum, maximum 2.0% tungsten, maximum 0.5% niobium, maximum 0.5% copper, maximum 0.5% vanadium, if necessary 0 to 15% Co, if necessary 0 to 0.20% Zr, if necessary 0.0001 to 0.008% boron, the remainder is nickel and the conventional impurities related to the process, with the nickel content being greater than 35%, with the Cr + Fe + Co ratio is (greater than) 25% (1) must be satisfied in order to obtain a good wear resistance and the fh (greater than) ratio 0 (2a) where fh = 6.49 + 3.88 Ti? 1.36 Al? 0.301 Fe (...).
    公开号:BR112016011060B1
    申请号:R112016011060-9
    申请日:2015-01-12
    公开日:2021-01-26
    发明作者:Heike Hattendorf
    申请人:Vdm Metals International Gmbh；
    IPC主号:
    专利说明:

    [0001] The present invention relates to a forged nickel-chromium-iron-titanium-aluminum alloy with very good wear resistance, at the same time, with good creep resistance, good resistance to high temperature corrosion and good processability.
    [0002] Nickel-chromium-titanium-aluminum hardening alloys, with different levels of nickel, chromium, titanium and aluminum have long been used for engine discharge valves. Good wear resistance, good heat resistance / creep resistance, good resistance to alternating stresses, as well as good resistance to corrosion at high temperature (in particular in exhaust gases) are required for this use.
    [0003] The DIN EN 10090 standard mentions for discharge valves, in particular, austenitic alloys, of which the nickel alloys 2.4955 and 2.4952 (NiCr20TiAl) have the greatest heat resistance and time stability of all the alloys mentioned in this standard . Table 1 shows the composition of the nickel alloys mentioned in DIN EN 10090, tables 2 to 4 show the tensile strengths, the elasticity limit of 0.2% and the reference values for time stability after 1000 hours.
    [0004] In the DIN EN 10090 standard, 2 alloys with a high nickel content are mentioned: a) NiFe25Cr20NbTi with 0.05 to 0.10% C, maximum 1.0% Si, maximum 1.0% Mn , maximum 0.030% P, maximum 0.015% S, 18.00 to 21.00% Cr, 23.00 to 28.00% Fe, 0.30 to 1.00% Al, 1, 00 to 2.00% Ti, 1.00 to 2.00% Nb + Ta, maximum 0.008% B and the remainder is Ni. b) NiCr20TiAl with 0.05 to 0.10% C, maximum 1.0% Si, maximum 1.0% Mn, maximum 0.020% P, maximum 0.015% S, 18.00 to 21.00% Cr, maximum 3% Fe, 1.00 to 1.80% Al, 1.80 to 2.70% Ti, maximum 0.2% Cu, maximum 2 0% Co, maximum 0.008% B and the remainder is Ni.
    [0005] NiCr20TiAl has significantly higher tensile strengths compared to NiFe25Cr20NbTi, 0.2% expansion limits and time stability at higher temperatures.
    [0006] EP 0.639.654 A2 publishes an iron-nickel-chromium alloy, consisting of (in% by weight) up to 0.15% C, up to 1.0% Si, up to 3.0% Mn, 30 to 49% of Ni, 10 to 18% by weight, of Cr, 1.6 to 3.0% of Al, in one or more elements of group IVa to Va with a total content of 1.5 to 8 , 0%, the rest is Fe and unavoidable impurities, with Al being an indispensable additive element and one or more elements from group IVa to Va already mentioned, which must satisfy the following formula in% in atoms: 0.45 <Al / (Al + Ti + Zr + Hf + V + Nb + Ta) <0.75
    [0007] WO 2008/007190 A2 publishes a wear-resistant alloy, consisting of (in% by weight) 0.15 to 0.35% of C, up to 1.0% of Si, up to 1.0% of 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 % up to 3% in sum Nb plus Ta, up to 0.015% B, the rest is Fe and unavoidable impurities, with Mo being + 0.5W <0.75%; Ti + Nb> 4.5% and 13 <(Ti + Nb) / C <50. The alloy is particularly useful for the production of flush valves for 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 primary carbides, however, causes processing problems during the production of this alloy as a forged alloy.
    [0008] In all the aforementioned alloys, heat resistance or resistance to creep in the range of 500oC to 900oC 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, heat resistance or creep resistance is also improved through high levels of mixed crystal fasteners, such as chromium, aluminum, silicon, molybdenum and tungsten, in the same way, as through a high carbon content.
    [0009] Regarding resistance to corrosion at high temperature, it should be noted that alloys with a chromium content around 20% form a layer of chromium oxide (Cr2O3) that protects the material. The chromium content is slowly spent during use in the field of application for the structure of the protective layer. Therefore, due to a higher chromium content, the useful life of the material improves, since a higher content of the chromium element forming the protective layer delays the time, in which the Cr content is under the critical limit and forms oxides other than Cr2O3, which are, for example, oxides containing iron and containing nickel.
    [00010] In order to process the alloy, in particular, in hot molding, it is necessary that at temperatures, in which the hot molding takes place, no phases are formed, which fix the material strongly, such as, for example, the phase y 'or y "and thus lead to the formation of cracks in hot molding. At the same time, these temperatures must be sufficiently below the solidification temperature of the alloy, to avoid melt bonding in the alloy.
    [00011] EP 1,464,718 A1 publishes a high strength heat resistant alloy for discharge valves, which has the following composition: 0.01 to 0.2% C, up to 1.0% Si, up to 1 , 0% Mn, up to 0.02% P, up to 0.01% S, 30 to 62% Ni, 13 to 20% Cr, up to 2.0% Mo, 0.01 to 3, 0% W, and the sum of Mo + 0.5 W should make up 1.0 to 2.5%,> 0.7 to <1.6% Al, 1.5 to 3.0% Ti , with the Ti / Al ratio being between 1.6 and 2.0%, 0.5 to 1.5% Nb, 0.001 to 0.1% B, the rest is iron and unavoidable impurities.
    [00012] Through EP 1,696,108 A1, a heat resistant alloy for discharge valves is known, which has the following composition: 0.01 to 0.15% of C, up to 2.0% of Si, up to 1, 0% Mn, up to 0.02% P, up to 0.01% S, 0.1 to 15% Co, 15 to 25% Cr, 0.1 to 10% Mo and / or 0, 1 to 5% of W, the sum of Mo + ^ W should be between 3 and 10%, 1.0 to 3.0% of Al, 2.0 to 3.5% of Ti, and the sum (in% in atoms) of Al + Ti must be between 6.3 and 8.5% and the Ti / Al ratio, 0.4 to 0.8. In addition, elements B and levels from 0.001 to 0.01%, Fe up to 3% are still contained, the remainder is nickel and unavoidable impurities.
    [00013] The objective on which the invention is based is to develop a forged nickel-chromium alloy, which has a better wear resistance than NiCr20TiAl, a similarly good resistance to heat / creep resistance like NiCr20TiAl, a good resistance to corrosion. like NiCr20TiAl a good processability similar to that of NiCr20TiAl. In addition, this must be profitable.
    [00014] This objective is solved by a forged nickel-chromium-iron-titanium-aluminum hardening alloy with very good wear resistance, with simultaneously good creep resistance, good resistance to high temperature corrosion and good processability with (in % by mass)> 18 to 26% chromium, 1.5 to 3.0% titanium, 0.6 to 2.0% aluminum, 7.0 to 40% iron, 0.005 to 0.10% carbon, 0.0005 to 0.050% nitrogen, 0.0005 to 0.030% phosphorus, maximum 0.010% sulfur, maximum 0.020% oxygen, maximum 0.70% silicon, maximum 2.0% of manganese, maximum 0.05% magnesium, maximum 0.05% calcium, maximum 0.5% molybdenum, maximum 0.5% tungsten, maximum 0.2% niobium, maximum 0.5% copper, maximum 0.5% vanadium, if necessary 0 to 15% Co, if necessary 0 to 0.20% Zr, if necessary 0.0001% to 0.0008% boron, optionally the following elements may still be contained in the alloy: Y 0 to 0.20% and / or La 0 to 0.20% and / or Ce 0 to 0, 20% and / or mixed metal of Cer 0 to 0.20% and / or Hf 0 to 0.20% and / or Ta 0 to 0.60%, the rest is nickel and the conventional impurities related to the process in levels of maximum 0.002% Pb, maximum 0.002% Zn, maximum 0.002% Sn, with a nickel content greater than 40% 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) to provide sufficient resistance at higher temperatures, with Ti, Al, Fe, Co, Cr and C being the concentration of the respective elements in% by mass and fh is expressed in%.
    [00015] Advantageous developments of the objective of the invention should be removed from the associated dependent claims.
    [00016] The expansion range for the chromium element is between> 18 and 26%, with the preferred ranges being adjustable as follows: -> 18 to 25% - 19 to 24% - 19 to 22%.
    [00017] The titanium content is between 1.5 and 3.0%. Preferably, Ti can be adjusted to the alloy within the expansion range, as follows: - 1.8 to 3.0%, - 2.0 to 3.0%, - 2.2 to 3.0%, - 2.2 to 2.8%.
    [00018] The aluminum content is between 0.6 and 2.0%, and here too, depending on the field of application 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%.
    [00019] The iron content is between 7.0 and 40%, and, depending on the field of application, the preferred levels can be adjusted within the following expansion ranges: - 7.0 to 35% - 8, 0 to 35% - 8.0 to 20% - 8.0 to 15% -> 11 to 15%.
    [00020] The alloy contains 0.005 to 0.10% carbon. Preferably, this can be adjusted on the alloy within the expansion range as follows: - 0.01 to 0.10% - 0.02 to 0.10% - 0.04 to 0.10% - 0.04 to 0 , 08%.
    [00021] This applies in the same way for the nitrogen element, which is contained in levels between 0.0005 and 0.05%. Preferred contents can be checked as follows: - 0.001 to 0.05% - 0.001 to 0.04% - 0.001 to 0.03% - 0.001 to 0.02% - 0.001 to 0.01%.
    [00022] The alloy also contains phosphorus in levels between 0.0005 and 0.030%. Preferred contents can be checked as follows: - 0.001 to 0.030% - 0.001 to 0.020%. The sulfur element is added to the alloy as follows: - maximum sulfur 0.010%.
    [00023] The oxygen element is contained in the alloy in contents of a maximum of 0.020%. Other preferred levels can be checked as follows: - maximum 0.010% - maximum 0.008% - maximum 0.004%.
    [00024] The Si element is contained in the alloy in contents of a maximum of 0.70%. Other preferred contents can be checked as follows: - maximum 0.50% maximum 0.20% - maximum 0.10%
    [00025] In addition, the Mn element is contained in the alloy in a maximum of 2.0%. Other preferred levels can be checked as follows: - at most 0.60% - at most 0.20% - at most 0.10%.
    [00026] The Mg element is contained in the alloy in contents of a maximum of 0.05%. Other preferred levels can be checked as follows: - at most 0.04% - at most 0.03% - at most 0.02% - at most 0.01%.
    [00027] The Ca element is contained in the alloy in contents of a maximum of 0.05%. Other preferred levels can be checked as follows: - at most 0.04% - at most 0.03% - at most 0.02% - at most 0.01%.
    [00028] The niobium element is contained in the alloy in contents of a maximum of 0.2%. Other preferred levels can be checked as follows: - maximum 0.10% - maximum 0.05%
    [00029] Molybdenum and tungsten are contained individually or in combination in the alloy with a maximum content of 0.5% each. Other preferred levels can be checked as follows: - Mo <0.50% - W <0.50% - Mo <0.10% - W <0.10% - Mo <0.05% - W <0, 05%.
    [00030] In addition, a maximum of 0.5% Cu may be contained in the alloy. The copper content can also be limited as follows: - Cu <0.10% - Cu <0.05% - Cu <0.015%.
    [00031] Furthermore, the alloy may contain a maximum of 0.5% vanadium.
    [00032] Furthermore, the alloy may contain, if necessary, between 0.0 and 15.0% cobalt which, furthermore, can still be limited as follows: -> 0.0 to 12.0% -> 0 , 0 to 10.0% -> 0.0 to 8.0% -> 0.0 to 7.0% -> 0.0 to 5.0% -> 0.0 to 2.0%.
    [00033] In addition, the alloy may contain, if necessary, between 0.0 and 0.20% zirconium which, furthermore, can still be limited as follows: - 0.01 to 0.20% - 0.01 0.15% - 0.01 to <0.10%.
    [00034] Furthermore, in the alloy, between 0.0001 and 0.008% of boron may be contained, if necessary. Other preferred contents can be as follows: - 0.0005 to 0.006% - 0.0005 to 0.004%.
    [00035] The nickel content must be above 35%. Preferred levels can be indicated as follows: -> 40% -> 45% -> 50% -> 55%.
    [00036] The following relationship between Cr and Fe and Co must be satisfied, in order to provide sufficient wear resistance of the alloy: Cr + Fe + Co> 25% (1) with Cr, Fe and Co being the concentration of respective elements in mass%.
    [00037] Other preferred ranges can be adjusted with Cr + Fe + Co> 26% (1a) Cr + Fe + Co> 27% (1b) Cr + Fe + Co> 28% (1c) Cr + Fe + Co> 29 % (1d)
    [00038] The following relationship between Ti, Al, Fe, Co, Cr and C must be satisfied, so that a sufficiently high resistance is given at higher temperatures: - h> 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 respective elements in% by mass and fh is expressed in%.
    [00039] Preferred ranges can be adjusted with fh> 1% (2b) fh> 3% (2c) fh> 4% (2d) fh> 5% (2e) fh> 6% (2f)
    [00040] Optionally, in the alloy the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb can be satisfied, so that a sufficiently good processability is given: 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 respective elements in% by mass and fver is expressed in%. Preferred ranges can be adjusted with fver = <5% (3b) fver = <3% (3c) fver = <0% (3d)
    [00041] Optionally, in the alloy, the yttrium element can be adjusted in levels from 0.0 to 0.20%. Preferably, Y can be adjusted on the alloy within the expansion range, as follows: - 0.01 to 0.20% - 0.01 to 0.15% - 0.01 to 0.10% - 0.01 to 0.08% - 0.01 to <0.045%.
    [00042] Optionally, in the alloy the lanthane element can be adjusted in levels of 0.0 to 0.20%. Preferably, La can be adjusted on the alloy within the expansion range, as follows: - 0.001 to 0.20% - 0.001 to 0.15% - 0.001 to 0.10% - 0.001 to 0.08% - 0.001 to 0 , 04% - 0.01 to 0.04%.
    [00043] Optionally, in the alloy the element Ce can be adjusted in levels of 0.0 to 0.20%. Preferably, Ce can be adjusted on the alloy within the expansion range, as follows: - 0.001 to 0.20% - 0.001 to 0.15% - 0.001 to 0.10% - 0.001 to 0.08% - 0.001 to 0 , 04% - 0.01 to 0.04%.
    [00044] Optionally, with the simultaneous addition of Ce and La, a mixed metal of Cer in levels of 0.0 to 0.20% can also be used. Preferably, the mixed Cer metal can be adjusted to the alloy within the expansion range, as follows: - 0.001 to 0.20% - 0.001 to 0.15% - 0.001 to 0.10% - 0.001 to 0.08% - 0.001 to 0.04% - 0.01 to 0.04%.
    [00045] Optionally, the alloy can also contain 0.0 to 0.20% hafnium. Preferred tracks can be checked out as follows. - 0.001 to 0.20% - 0.001 to 0.15% - 0.001 to 0.10% - 0.001 to 0.08% - 0.001 to 0.04% - 0.01 to 0.04%.
    [00046] Optionally, the alloy can also contain 0.0 to 0.60% tantalum - 0.001 to 0.60% - 0.001 to 0.40% - 0.001 to 0.20% - 0.001 to 0.15% - 0.001 to 0.10% - 0.001 to 0.08% - 0.001 to 0.04% - 0.01 to 0.04%.
    [00047] Finally, as impurities can still be given the elements lead, zinc and tin in levels as follows: Pb maximum 0.002% Zn maximum 0.002% Sn maximum 0.002%.
    [00048] The alloy according to the invention is preferably cast in the vacuum induction oven (VIM), but can also be cast open, followed by a treatment in a VOD or VLF installation. After block casting or optionally as continuous casting, the alloy is optionally annealed at temperatures between 600oC and 1100oC for 0.1 hour (h) up to 100 hours, optionally under a protective gas, such as, for example, argon or hydrogen, followed by cooling in air or in the moving annealing atmosphere. Then, a re-melting can be done using VAR or ESU, optionally followed by a second re-melting process via VAR or ESU. Next, the blocks are optionally annealed at temperatures between 900oC and 1270oC for 0.1 to 70 hours, then they are heat-transformed, optionally with one or more intermediate anneals between 900oC and 1270oC for 0.05 to 70 hours. Hot processing can be carried out, for example, by forging or hot rolling. The surface of the material in the entire process optionally (also several times) can be removed, however and / or at the end of the cleaning chemically (for example, through cauterization and / or mechanically (for example, through machining, through radiation or the hot molding process can be carried out in such a way that the semi-finished product is then already recrystallized with grain sizes between 5 and 100 μm, preferably between 5 and 40 μm. , then, it is annealed in solution in the temperature range of 700oC to 1270oC for 0.1 minute to 70 hours, optionally under protective gas, such as, for example, argon or hydrogen, followed by air cooling, in the annealing atmosphere in motion or in the water bath. After the completion of the hot molding, a cold molding (for example, lamination, drawing, through forging, stamping, pressing) with degrees of formation of up to 98% for the desired semi-finished product form, optionally with intermediate annealing between 700oC to 1270oC for 0.1 minute to 70 hours, optionally under protective gas, such as, for example, argon or hydrogen, followed by cooling to the air, in the moving annealing atmosphere or in the water bath. Optionally, however, in the cold molding process and / or after the last annealing, chemical and / or mechanical cleaning (for example, radiation, grinding, turning, scraping, brushing) can be carried out on the material surface.
    [00049] The definitive properties reach the alloys according to the invention or the parts made from them, through a hardening annealing between 600oC and 900oC for 0.1 to 300 hours, followed by air cooling and / or in the oven. Through such hardening annealing, the alloy according to the invention hardens through the separation of a finely dispersed Y 'phase. Alternatively, a two-stage annealing can be carried out, in which the first annealing is carried out in the range of 800oC to 900oC for 0.1 to 300 hours, followed by air cooling and / or oven cooling and a second annealing between 600oC and 800oC for 0.1 to 300 hours, followed by air cooling.
    [00050] The alloy according to the invention can be well produced and used in the forms of strip, plate, bar, wire, welded tube with longitudinal seam and seamless tube.
    [00051] 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, in particular, between 5 and 40 μm.
    [00052] The alloy according to the invention can be well processed by means of forging, compression, hot extrusion, hot rolling and similar processes. Through these processes, among others, components such as valves, hollow valves or dowels can be manufactured.
    [00053] The alloy according to the invention should preferably be used in areas of valves, in particular, discharge valves for combustion engines. But it is also possible to use it in gas turbine components, such as locking pins, in springs and in turbochargers.
    [00054] Parts produced from the alloy according to the invention, in particular, for example, valves or valve seat surfaces, can be subjected to other surface treatments, such as, for example, a nitration, in order to further increase wear resistance. Tests performed:
    [00055] In order to measure the wear resistance, sliding wear tests were carried out on a pin (pin) on a test bench on a disk (Optimol tribometer IV SR). The radius of the pins in the shape of a semicircle, polished in a specular manner was 5 mm. The pins were produced from the material to be tested. The disc consisted of cast iron with a martensitic matrix approved with secondary carbides within a network of eutectic carbides 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 with a load of 20 N with a path of one mm, with a frequency of 20 Hz and an atmospheric humidity of about 45% with different temperatures.
    [00056] Details of the tribometer and the test procedure are described in "C. Rynio, H. Hattendorf, J. Klower, H.-G. Eggeler, Mat.- wiss. U. Werkstofftech. 44 (2013), 825. During the test, the friction coefficient, the linear displacement of the pin towards the disc (as a measure for the general linear wear of pin and disc) and the resistance to electrical contact between pin and disc are measured continuously. dynamometric modules, which are hereinafter referred to as (a) or (n). These provide quantitatively slightly different, but qualitatively similar results. The dynamometric module (n) is the most accurate. Upon completion of a test, the volumetric loss of the pin was measured and used as a measure for the position for wear resistance of the pin material.
    [00057] Heat resistance was determined in a hot tensile test in accordance with DIN EN ISO 6892-2. In this case, the elastic limit Rp0.2 and the tensile strength Rm were determined: the tests were carried out on circular samples with a diameter of 6 mm in the measuring range and with an initial measurement length L0 of 30 mm. Sampling was carried out transversely to the deformation direction of the semi-finished product. The strain rate with Rp0.2 was 8.33 10-5 1 / s (0.5% / min) and with Rm, 8.33 10-4 1 / s (5% / min).
    [00058] The sample was embedded in a tensile testing machine and without load was heated with a tensile force to the desired temperature. After reaching the test temperature, the load sample was kept for one hour (600oC) or for two hours (700oC to 1100oC) for temperature compensation. Then, the sample was loaded so much with a tractive force that the desired expansion speeds were maintained and the test started.
    [00059] The creep resistance of a material improves with increasing heat resistance. Therefore, heat resistance is also used to assess the creep resistance of different materials.
    [00060] Resistance to corrosion at higher temperatures was determined in an oxidation test at 800oC in air, the test being interrupted every 96 hours and the measurement changes of the samples were determined through oxidation. In the test, the samples were placed in ceramic bowls, so that the optionally popped oxide was collected and the mass of the popped oxide can be determined by weighing the bowl containing the oxides. The sum of the mass of the popped oxide and the variation in the mass of the sample is the variation in the gross mass of the sample. The specific variation in mass is the variation in mass related to the surface of the samples. These are referred to below as net for the specific variation of the net mass, but for the specific variation of the gross mass, mspall for the specific variation of the mass of the cracked oxides. The tests were performed on samples about 5 mm thick. From each load, 3 samples were stored, the indicated values are the average values of those 3 samples.
    [00061] The phases that occur in equilibrium were calculated with the Thermotech JMatPro program for several alloy variants. As a database for the calculations, the TTNI7 database was used for Thermotech nickel-based alloys. With this, phases can be identified, whose formation in the application area weakens the material. In addition, temperature ranges can be identified, in which, for example, hot molding should not be carried out, since in this phase phases are formed, which strongly fix the material and, thus, lead to the formation of cracks in the molding at hot. For good processability, in particular, in hot molding, such as, for example, hot rolling, forging, settlement, hot extrusion and other processes, a sufficiently wide temperature range must be available, in which they do not form. such phases. Description of properties
    [00062] The alloy according to the invention must have, according to the problem equation, the following properties: a better resistance to wear against NiCr20TiAl a resistance to heat / resistance to creep similarly good, such as NiCr20TiAl a good resistance to corrosion at least equal to NiCr20TiAl good processability similar to NiCr20TiAl.
    [00063] In addition, it must be profitable. Wear resistance
    [00064] The new material must have better wear resistance than the reference alloy NiCr20TiAl. In addition to this material, stelite 6 was also tested for comparison. Stelite 6 is a highly wear-resistant cobalt-based cast alloy with a network of tungsten carbides, which consist of about 28% Cr, 1% Si, 2% Fe, 6% W, 1.2% C, the rest is Co, but due to its high carbide content, it must be poured directly into the desired mold. Due to its tungsten carbide network, stelite 6 achieves a high hardness of 438 HV30, which is very advantageous for wear. The alloy "E" according to the invention should approach as much as possible the loss of volume of stelite 6. The objective is, in particular, to reduce the wear at high temperature between 600 and 800oC, which the relevant temperature range is , for example, for an application as a discharge valve. Therefore, in particular, the following criteria must be applied to the "E" alloys according to the invention:
    [00065] Average volume loss value (alloy "E") <0.50 x average volume loss value (reference NiCr20TiAl) at 600oC or 800oC. (4a).
    [00066] In the "low temperature range" of wear, the volume loss cannot increase disproportionately. Therefore, the following criteria must apply additionally.
    [00067] Average value of volume loss ("E" alloy) <1.30 x average value of volume loss (NiCr20TiAl reference) at 25oC and 300oC (4b)
    [00068] If in a series of measurements there is both a volume loss of NiCr20TiAl for an industrial-scale load and a reference laboratory load, so that the average value of these two loads falls into inequalities (4a) or (4b) . Heat resistance / creep resistance
    [00069] Table 3 shows the lower end of the dispersion band of the 0.2% elastic limit for NiCr20TiAl in the state hardened at temperatures between 500 and 800oC, Table 2, the lower end of the tensile strength dispersion band. .
    [00070] The elastic limit of 0.2% of the new alloy must fall within this value range to 600oC or at 800oC it must not pass this value range below 50 MPa, in order to obtain a satisfactory strength. That is, in particular, the following values must be obtained: 600oC: elastic limit Rpo, 2> 650 MPa (5a) 800oC: elastic limit Rpo, 2> 390 MPa (5b)
    [00071] This is achieved, in particular, if 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 respective elements in% by mass and fh is expressed in%. Corrosion resistance:
    [00072] The alloy according to the invention must have a resistance to corrosion to air similar to that of NiCr20TiAl. Processability
    [00073] In nickel-chromium-iron-titanium-aluminum alloys, heat resistance or resistance to creep in the range of 500oC to 900oC is based on the addition of aluminum, titanium and / or niobium, which lead to phase separation Y 'and / or Y ". If the hot molding of these alloys is carried out in the separation range of these phases, then there is a risk of crack formation. The hot molding, therefore, should preferably be carried out using the Tsy solution temperature. '(or Tsy ") of these phases. In order for a sufficient temperature range to be available for hot molding, the Tsy '(or Tsy ") solution temperature should be less than 1020oC.
    [00074] This is satisfied, in particular, if 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 TiAl2 - 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 respective elements in mass% and fver is expressed in%. Examples: Production:
    [00075] Tables 5a and 5b show the analysis of the molten loads on the laboratory scale together with some molten loads on an industrial scale applied for comparison, according to the current state of the art (NiCr20TiAl). The charges according to the current 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 on an industrial scale with a G. 250212 is NiCr20TiAl, but fused as a laboratory charge and serves as a reference.
    [00076] The ingots of the vacuum-cast alloys on a laboratory scale in table 5a and b were annealed between 1100oC and 1250oC for 0.1 to 70 hours and hot rolled using hot cylinders and other intermediate anneals between 1100oC and 1250oC for 0, 1 to 1 hour for 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 necessary samples for measurements were produced.
    [00077] The comparative charges cast on an industrial scale were cast by means of VIM and poured to form ingots. These ingots were remelted by means of ESU. These ingots were annealed between 1100oC and 1250oC for 0.1 minutes at 70 hours, optionally under protective gas, such as, for example, argon or hydrogen, followed by cooling in air, in the moving annealing atmosphere or in the water bath. and by means of hot rolling and other intermediate annealing between 1100oC and 1250oC for 0.1 to 20 hours, the ingots were hot rolled to a final diameter between 17 and 40 mm. The temperature conduction in hot rolling was such that the plates were recrystallized.
    [00078] All alloy variants typically had a grain size of 21 to 52 μm (see table 6).
    [00079] After the samples were produced, they were hardened by annealing at 850oC for 4 hours / cooling in air, followed by annealing at 700oC for 16 hours / cooling in air.
    [00080] Table 6 shows the hardness of Vicker HV30 before and after hardening annealing. The HV30 hardness in the hardened state for all alloys, with the exception of the 250330 load, is in the range 366 to 416. The 250330 load has a slightly lower hardness of 346 HV30.
    [00081] For the loads in the examples in Table 5a and 5b, the following properties are compared: wear resistance with the aid of a sliding wear test, heat resistance / creep resistance with the aid of hot tensile tests resistance to corrosion with the aid of an oxidation test and processability with phase calculations
    [00082] In this regard, cost effectiveness is observed. Wear resistance
    [00083] Wear tests were carried out at 25oC, 300oC, 600oC and 800oC in alloys according to the current state of the art and in several laboratory fusions. Most of the tests were repeated several times. Next, mean values and standard deviations were determined.
    [00084] Table 7 shows the average values + standard deviations of the measurements made. If the standard deviation is missing, then it is a single value. The composition of the charges is described approximately in table 7 in the alloy column for guidance. In addition, the maximum values for the volume loss of the alloys according to the invention of the inequalities (4a) for 600 or 800oC and (4b) for 25oC and 300oC are represented in the last line.
    [00085] Figure 1 shows the volume loss of the NiCr20TiAl pin load 320776 according to the current state of the art as a function of the test temperature, measured with 20 N, 1 mm path, 20 Hz and with the dynamometric module ( The). The tests at 25 and 300oC were carried out for one hour and the tests at 600 and 800oC were carried out for 10 hours. The volume loss up to 600oC decreases a lot with the temperature, that is, the wear resistance visibly improves at higher temperatures. In the high temperature range at 600 and 800oC there is a comparatively less volume loss and, therefore, less wear, which is based on the formation of a so-called "glaze" layer between the pin and the disc. This "glaze" layer consists of compacted metal oxides and pin and disc material. The greatest loss of volume at 25oC and 300oC despite the short time around factor 10 is based on the fact that the "glaze" layer cannot completely form at these temperatures. At 800oC the volume loss increases slightly again due to the increase in oxidation.
    [00086] Figure 2 shows the volume loss of the NiCr20TiAl pin load 320776 according to the current state of the art as a function of the test temperature measured with 20 N, 1 mm path, 20 Hz and with the dynamometric module (n ). For NiCr20TiAl load 320776 there is qualitatively the same behavior as with the force module (a): the volume loss up to 600oC decreases a lot with the temperature, and the values at 600 and 800oC are still lower than those measured with the dynamometric module (a). In addition, in Figure 2, the values measured in stelite 6 are represented. Stelite 6 shows a better wear resistance (= less loss of volume) at all temperatures up to 300oC than the comparative alloy NiCr20TiAl load 320776.
    [00087] Volume losses at 600 and 800oC are very low, so that the differences between different alloys can no longer be reliably measured. For this reason, a test at 800oC with 20 N for 2 hours + 100 N for 5 hours, 1 mm, 20 Hz travel was performed with the dynamometric module (n), to produce a slightly higher wear even in the high temperature range . The results are shown in Figure 3 together with the volume losses measured with 20 N, 1 mm path, 20 Hz and dynamometric module (n) with different temperatures. In this way, the volume loss in the high temperature range of wear has increased markedly.
    [00088] The comparison of the different alloys was carried out with different temperatures. In Figures 4 to 8, the laboratory loads are characterized by an L. The most important variation in relation to the industrial scale load 320776 is indicated in the Figures in addition to the number of laboratory loads with element and rounded value. The exact values are found in tables 5a and 5b. Rounded values are used in the text.
    [00089] Figure 4 shows the pin volume loss for different laboratory loads compared to NiCr20TiAl, load 320776 and stelite 6 to 25oC after 1 hour, measured at 20 N, 1 mm path, 20 Hz with dynamometric module (a) and (n). The values with the dynamometer module (n) were systematically lower than those with the dynamometer module (a). Considering this, then it must be recognized that NiCr20TiAl as laboratory load 250212 and as industrial scale load 320776 had a similar volume loss in terms of measurement accuracy. Laboratory loads can therefore be compared based on wear measurements directly with industrial scale loads. The 250325 load according to the invention with about 6.5% Fe showed at 25oC a lower volume loss than the maximum value of (4b) for the two dynamometric modules (see table 7). The volume loss of charge 250206 according to the invention with 11% Fe tended to be in the upper dispersion range of charge 320776, but the mean value was also less than the maximum value of (4a). The load 250327 according to the invention with 29% Fe showed a slightly increased volume loss in measurements with the dynamometric module (n), but the average value here was also less than the maximum value of (4b) for both dynamometric modules. The laboratory charges containing Co showed, on the contrary, a loss of volume that tended to be reduced, which at 9.8% of Co with the dynamometric module (n) with 1.04+ 0.01 mm3 is exactly within the charge dispersion range. 320776. With 30% Co, it was possible to recognize, afterwards, with 0.79 + 0.06 mm3 a clear reduction in volume loss, which, afterwards, with the load 250330 increased slightly again by the addition of 10% Fe with 0.93 + 0.02 mm3. The increase in the Cr content with the load 250326 to 30% in relation to the 20% of the load 320776 produced an increase in volume wear to 1.41 + 0.18 mm3 (dynamometric modulus (n)), but which was also below of the maximum value of (4a).
    [00090] Figure 5 shows the pin volume loss for alloys with different carbon contents compared to NiCr20TiAl, load 320776 at 25oC, measured at 20 N, 1 mm path, 20 Hz with dynamometric module (a) after 10 hours. Neither through a reduction in the carbon content to 0.01% with the 250211 load, but also through an increase to 0.211% with the 250214 load, there was no variation in the volume loss compared to the 320776 load.
    [00091] Figure 6 shows the loss of pin volume for various alloys compared to NiCr20TiAl, load 320776 at 300oC with 20 N, 1 mm path, 20 Hz after 1 hour, measured with dynamometric modules (a) and (n). The values with the dynamometric module (n) are systematically lower than those with the dynamometric module (a). Considering this below, then it is recognized that at 300oC the stelite 6 was worse than the load 320776. In laboratory fusions 250329 and 250330 containing Co, no reduction in wear volume was observed, such as at room temperature, but yes, this was in the range of the wear volume of NiCr20TiAl, load 320776 and therefore did not show any increase, as in stelite 6. Contrary to the behavior at room temperature, laboratory fusions 250206 and 250327 containing Fe showed a loss of volume, which decreases with the increase of the Fe content, which, with this, was clearly below the maximum value (4b). The laboratory load 250326 with a 30% Cr content had a volume loss in the NiCr20TiAl load range, 320776.
    [00092] Figure 7 shows the pin volume loss for various alloys compared to NiCr20TiAl, load 320776 at 600oC, measured at 20 N, 1 mm path, 20 Hz and with the dynamometric module (a) and (n) after 10 hours. The values with the dynamometric module (n) were systematically lower than with the dynamometric module (a). It is recognized that also in the high temperature range of wear, the reference laboratory load 250212 in relation to the NiCr20TiAl with 0.066 + 0.02 mm3 had a comparable volume loss, as did the industrial scale load 320776 with 0.053 + 0 , 0028 mm3. Laboratory loads, therefore, can also be compared in relation to wear measurements in this temperature range directly with industrial scale loads. Stelite 6 showed a reduced volume loss around factor 3 of 0.009 + 0.002 mm3 (dynamometric module (n)). In addition, it was found that neither through a reduction in the carbon content to 0.01% with the 250211 load, but also through an increase to 0.211% in the 250214 load, it was possible to obtain a variation in the weight loss in comparison on load 320776 and 250212 (dynamometric module (a)). Also the addition of 1.4% manganese in cargo 250208 or 4.6% tungsten in cargo 250210 did not lead to any significant variation in volume loss compared to cargo 320776 and 250212. Cargo 250206 according to invention with 11% iron showed a clear reduction in volume loss with 0.025 + 0.003 mm3 compared to the load 320776 and 250212 to 0.025 + 0.003 mm3, which was less than the maximum value of (4a). In the load 250327 according to the invention with 29% iron, the loss of volume with 0.05 mm3 was comparable with that of the load 320776 and 250212. Also in the laboratory load 250209 with 9.8% of Co, the loss of volume with 0.0642 mm3 was comparable to that of load 320776 and 250212. In laboratory loads 250329 with 30% Co and 250330 with 29% Co and 10% Fe, the loss of volume with 0.020 and 0.029 mm3 was clearly less than that of load 320776 and 250212. The volume loss of load 250326 decreased to a similarly low value of 0.026 mm3 through a Cr content 30% higher.
    [00093] Figure 8 shows the loss of pin volume for the various alloys in comparison with the NiCr20TiAl load 320776 at 800oC with 20 N for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz, measured with the dynamometric module (n). Also at 800oC, it was confirmed that in the high wear temperature range, the reference laboratory load 250212 in relation to NiCr20TiAl with 0.292 + 0.016 mm3 had a comparable volume loss, as did the load 320776 on an industrial scale with 0.331 + 0.081 mm3 . The laboratory loads could be compared, therefore, based on wear measurements also at 800oC, directly with the loads on an industrial scale. The load 250325 according to the invention with 6.5% iron showed a clear reduction in volume loss with 0.136 + 0.025 mm3 compared to the load 320776 and 250212 below the maximum value of 0.156 mm3 of (4a). In load 250206 according to the invention with 11% iron, an additional reduction in volume loss was found with 0.057 + 0.007 mm3 compared to load 320776. In load 250327 according to the invention with 29% Fe, the volume loss was 0.043 + 0.02 mm3. These two times are values, which were clearly below the maximum value of 0.156 mm3 of (4a). Also in the laboratory load 250209 with 9.8% Co, the volume loss of 0.144 + 0.012 mm3 fell to a similar value, as in the laboratory load 250325 with 6.5% iron - clearly below the maximum value 0.156 mm3 of (4a) -. In laboratory load 250329 with 30% Co, there was an additional reduction in volume loss to 0.061 + 0.005 mm3. In the laboratory load 250330 with 29% Co and 10% Fe, the volume loss fell again through the addition of Fe with 0.021 + 0.001 mm3. The volume loss of charge 250326 decreased to a similarly low value of 0.042 + 0.011 mm3, as did that of charge 250206 with 11% iron through an increased Cr content to 30%.
    [00094] Particularly at the values measured at 800oC, it was found that the loss of pin volume in the wear test could be greatly reduced through an Fe content between> 3 and 40%, so that at one of the two temperatures 600 or 800oC, this was less than or equal to 50% of the volume loss of NiCr20TiAl (4a). The alloys according to the invention with an Fe content of> 3 to 40%, also at 25oC and 300oC, satisfy the inequalities (4b). Particularly at 300oC, the alloys according to the invention even had a volume loss reduced by more than 30%. An iron content of> 3 to 40% also decreased the costs of metals for this alloy.
    [00095] In laboratory load 250209 with 10% Co, the volume loss at 800oC decreased to 0.144 + 0.012 mm3 below the maximum value of (4a). At 25, 300 and 600oC there was no increase in wear. In laboratory loading 250329 with 30% Co, the volume loss at 800oC decreased again sharply to 0.061 + 0.005 mm3 below the maximum value of (4a). The same was verified at 600oC with a reduction to 0.020 mm3 below the maximum value of (4a). At 25oC, the laboratory load 250329 with 30% Co showed a reduction to 0.93 + 0.02 mm3 with dynamometric module (n). Even at 300oC, this 0.244 mm3 laboratory load showed wear similar to that of the reference load 320776 and 250212, quite unlike the stelite cobalt-based alloy 6, which at that temperature showed a volume loss markedly higher than the reference load 320776 and 250212. In the laboratory load 250330, through the addition of 10% iron, a further reduction in wear at 800oC to 0.021 + 0.001 mm3 was obtained in addition to 29% Co. From the cost point of view, limiting the optional cobalt content to values between 0 and 15% is advantageous.
    [00096] Load 250326 with 30% Cr also showed, at 800oC, a reduction in volume loss to 0.042 + 0.011 mm3 and also at 600oC, to 0.026 mm3, both below the respective maximum value of (4a). At 300oC, the volume loss with 0.2588 mm2 was also below the maximum value of (4a), as well as at 25oC with for 1.41 + 0.18 mm3 (dynamometric module (n)), of so that chromium contents between 18 and 31% are advantageous, in particular, for wear at higher temperatures.
    [00097] In Figure 9, the pin volume loss is applied to the various alloys in table 7 at 800oC with 20 N for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz path, measured with the dynamometric module (n) together with the sum Cr + Fe + Co of the formula (1) for very good wear resistance. It can be recognized that the loss of volume at 800oC was all the less the greater the sum of Cr + Fe + Co and vice versa. The Cr + Fe + Co formula is> 25% is, therefore, a criterion for very good wear resistance in the alloys according to the invention.
    [00098] NiCr20TiAl alloys of loads 320776 and 250212 according to the current state of the art had a sum of Cr + Fe + Co of 20.3% or 20.2%, both are less than 25% and met the requirements criteria (4a) and (4b) for very good wear resistance, but in particular not criteria (4a) for good wear resistance at high temperature. Loads 250211, 250214, 250208 and 250210 did not, in particular, meet the criteria (4a) for good wear resistance at high temperature and had a sum of Cr + Fe + Co of 20.4%, 20.2% , 20.3% or 20.3%, all less than 25%. The loads 250325, 250206, 250327, 250209, 250329, 250330 and 250326 with additions of Fe and Co or with an increased content of Cr, in particular the chambers 250325, 250206 and 250327 according to the invention, met the criteria (4a ) in any case to 800oC, partially even additionally to 600oC 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 satisfied equation (1) for very good wear resistance. Heat resistance / creep resistance
    [00099] Table 8 shows the elongation limit Rp0.2 and the tensile strength Rm for the ambient temperature (RT) for 600oC and 800oC. In addition, the measured grain sizes and values for fh are represented. Additionally, in the last line the minimum values of the inequalities (5a) and (5b) are shown.
    [000100] Figure 10 shows the elasticity limit Rp02 and the tensile strength Rm for 600oC, Figure 11 for 800oC. The loads 321863, 321426 and 315828 melted on an industrial scale had, for the elasticity limit Rp02 at 600oC, values between 841 and 885 MPa and at 800oC, values between 472 and 481 MPa. The reference laboratory load 250212, with an analysis similar to that of industrial scale loads, had an aluminum content slightly above 1.75%, which at 600oC led to an elasticity limit Rp02 slightly above 866 MPa and 800oC of 491 MPa.
    [000101] At 600oC, as shown in table 8, the elasticity limits Rp0.2 of all laboratory loads (L), therefore, also of the loads according to the invention and of all industrial scale loads (G ), were greater than 650 MPa, therefore, criterion (5a) was satisfied.
    [000102] At 800oC, as shown in table 8, the elasticity limits Rp0.2 of all laboratory loads (L), therefore, also of the loads according to the invention (E) and all loads in scale industrial (G), were greater than 390 MPa, therefore, the inequality (5b) was satisfied. The load 250327 with 29% Fe, however, barely satisfied this inequality, since, as shown by the observation of laboratory load 250212 (reference, similar to Fe loads on an industrial scale below 3%) or also of loads in industrial scale and loads 250325 according to the invention (6.5% Fe), 250206 (11% Fe) and 250327 (29% Fe), an increasing Fe content of the alloy decreased the elasticity limit Rp0, 2 in the tensile test (see also Figure 11). Therefore, a 40% Fe content of the alloy should be considered as an upper limit for the alloy according to the invention.
    [000103] Observation of laboratory load 250212 (reference, similar to loads on an industrial scale, without addition of Co) or also of loads on an industrial scale and loads 250209 (9.8% of Co) and 250329 (30% of Co) showed that a 9.8% Co content increased the elasticity limit Rp0.2 in the tensile test at 800oC to 526 MPa, or another increase to 30% of Co led again to a slight decrease to 489 MPa ( see also Figure 11). Therefore, an alloy content of up to 15% of Co in the alloy according to the invention is advantageous, in order, in particular, with high iron contents, to increase the elasticity limit Rp0.2 to 800oC to more than 390 MPa. A higher Co content no longer has any advantage, since it is less effective than the first 15% and, finally, leads again to a slight reduction in the yield strength. Also, contents of more than 15% of Co increase costs above the desired grade. Therefore, an alloy content of 15% Co should be considered as an upper limit for the alloy according to the invention.
    [000104] The laboratory load 250326 showed that, with an addition of 30% Cr, the elastic limit Rp0.2 in the tensile test at 800oC decreased to 415 MPa, which was still clearly above the minimum value of 390 MPa . Therefore, an alloy content of 31% Cr should be considered as an upper limit for the alloy according to the invention.
    [000105] In Figure 12, the elasticity limit Rp0,2 and fh, calculated according to formula (2), is represented for good heat resistance or creep resistance for the various alloys in table 8 at 800oC. It can be clearly recognized that fh within the scope of measurement accuracy, like the elasticity limit, rises and falls at 800oC. In this way, fh describes the elasticity limit Rp0.2 at 800oC. A fh> 0 is necessary to obtain a heat resistance or satisfactory creep resistance, as observed, in particular, in the load 250327 with Rp0.2 = 391 MPa, a value that is just over 390 MPa. This load has fh = 0.23% also a value that is slightly higher than the minimum value of 0%. Alloys 250325, 250206 and 250327 according to the invention all have a fh> 0%. Corrosion resistance:
    [000106] Table 9 shows the variations in mass after an oxidation test at 800oC in air after 6 cycles of 96 hours, therefore, a total of 576 hours. Table 9 shows the variation in gross specific mass, the variation in net specific gravity and the variation in specific gravity of the oxides that are cracked after 576 hours. The exemplified loads of the alloys according to the current state of the NiCr20TiAl technique, loads 321426 and 250212 showed a variation of specific gross mass of 9.69 or 10.84 g / m2 and a variation of specific net mass of 7.81 or 10 , 54 g / m2. Load 321426 showed insignificant crackling. The loads 250325 (6.5% Fe), 250206 (11% Fe) and 250327 (29% Fe) according to the invention showed a variation in specific mass from 9.26 to 10.92 g / m2 and a variation in net specific gravity from 9.05 to 10.61 g / m2, which are in the range of NiCr20TiAl reference alloys and, as required, are not worse. As a result, an Fe content of> 3 to 40% does not negatively influence oxidation resistance. Loads 250209 containing Co (9.8% Co) and 250329 (30% Co) also had a gross specific gravity variation of 10.05 or 9.91 g / m2 and a net specific gravity variation of 9, 81 or 9.71 g / m2, which were also in the range of NiCr20TiAl reference alloys and, as required, were no worse than these. In the same way, the load 250330 (29% Co, 10% Fe) behaved with a variation of 9.32 g / m2 gross density and with a variation of 8.98 g / m2 net density. As a result, a Co content of up to 30% does not negatively influence oxidation resistance. The 250326 filler with an increased Cr content of 30% had a variation of 6.74 g / m2 gross mass and a variation of 6.84 g / m2 specific gravity, which were below the range of alloys NiCr20TiAl reference. A Cr content of 30% improved resistance to oxidation.
    [000107] All alloys according to table 5b contain Zr, which serves as a reactive element to improve corrosion resistance. Optionally, other reactive elements can be added, such as Y, La, Ce, mixed metal of Cer, Hf, whose effectiveness should be evaluated as similar to Zr. Processability
    [000108] Figure 13 shows the phase diagram of the NiCr20TiAl load calculated with JMatPro according to the current state of the art. Below the Tsy 'solution temperature of 959oC, the Y' phase is formed, for example, with a proportion of 26% at 600oC. Soon after, the phase diagram shows the formation of Ni2M (M = Cr) below 558oC with proportions of up to 64%. This phase, however, is not observed when using this material with the combinations of temperature of use and time that occur in practice and, therefore, should not be considered. Additionally, Figure 13 also shows the range of existence of various carbides and nitrides, but which do not prevent hot molding at these concentrations. Hot molding can be carried out just above the Tsy 'solution temperature, which, for a sufficient temperature range to be available below the solidification temperature of 1310oC for hot molding, should be less than or equal to 1020oC.
    [000109] For the alloys in table 5a and 5b, therefore, the phase diagrams and the solution temperature Tsy 'recorded in table 5a were calculated. For the compositions in tables 5a and 5b, the value for fver was also calculated according to formula (3). fver is higher, the higher the temperature of Tsy 'solution. All the alloys in table 5a, including the alloys according to the invention, have a calculated Tsy 'solution temperature, less than or equal to 1020oC and satisfy the criterion (3a): fver <7. Inequality fver <7% (3a ), therefore, is a good criterion for obtaining a sufficiently large hot molding range and, therefore, good processability of the alloy.
    [000110] The claimed limits for the "E" alloys according to the invention can be substantiated individually as follows:
    [000111] Very low Cr levels mean that the Cr concentration when using the alloy in a corrosive atmosphere decreases very quickly below the critical limit, so that no closed chromium oxide layer can be formed anymore. Therefore, 18% Cr is the lower limit for chromium. Very high Cr levels increase the temperature of the Tsy solution too much, so that the processability clearly worsens. Therefore, 31% are considered an upper limit.
    [000112] Titanium increases the resistance to high temperature at temperatures in the range up to 900oC promoting the formation of the Y 'phase. In order to obtain sufficient strength, at least 1.0% is required. Very high titanium contents increase the temperature of the Tsy 'solution too much, so that the processability clearly worsens. For this reason, 3.0% are considered an upper limit.
    [000113] Aluminum increases the resistance to high temperature at temperatures in the range up to 900oC promoting the formation of the Y 'phase. In order to obtain sufficient strength, at least 0.6% is required. Very high aluminum contents increase the temperature of the Tsy 'solution too much, so that the processability worsens considerably. For this reason, 2.0% are considered an upper limit.
    [000114] Iron, in particular, increases wear resistance in the high temperature range. This also lowers costs. In order to obtain sufficient wear resistance and sufficient cost reduction, at least> 3.0% are required. Very high iron contents decrease the elasticity limit too much, in particular, at 800oC. Therefore, 40% are considered as an upper limit.
    [000115] 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 through the excessive formation of primary carbides.
    [000116] A minimum content of 0.0005% of N is necessary for reasons of cost, the N is limited to a maximum of 0.050%, since this element reduces the processability through the formation of thick carbon nitrides.
    [000117] The phosphorus content should be less than or equal to 0.030%, since this surfactant element impairs the resistance to oxidation. A very low phosphorus content increases costs. Therefore, the phosphorus content is> 0.0005%.
    [000118] Sulfur contents should be adjusted as low as possible, as this surfactant element impairs oxidation resistance and processability. Therefore, a maximum of 0.010% of S.
    [000119] The oxygen content must be less than or equal to 0.020%, in order to guarantee the production capacity of the alloy.
    [000120] Very high levels of silicon hinder processability. Therefore, the Si content is limited to 0.70%.
    [000121] Manganese is limited to 2.0%, as this element reduces resistance to oxidation.
    [000122] Already very low Mg and / or Ca levels improve processing through sulfur lashing, thus avoiding the occurrence of low melting NiS eutectic. In the case of very high levels, intermetallic Ni-Mg phases or Ni-Ca phases may occur, which again significantly worsen the processability. Therefore, the Mg content or the Ca content is respectively limited to a maximum of 0.05%.
    [000123] Molybdenum is limited to a maximum of 2.0%, as this element reduces resistance to oxidation.
    [000124] Tungsten is limited to a maximum of 2.0%, as this element also reduces resistance to oxidation and with the possible carbon content in forged alloys it has no measurable positive effect on wear resistance.
    [000125] Niobium increases resistance to high temperature. Higher levels increase costs too much. Therefore, the upper limit is set at 0.5%.
    [000126] Copper is limited to a maximum of 0.5%, as this element reduces resistance to oxidation.
    [000127] Vanadium is limited to a maximum of 0.5%, as this element reduces resistance to oxidation.
    [000128] Cobalt increases wear resistance and heat resistance / creep resistance. Therefore, it can optionally be contained in this alloy between 0 and 15%. Cobalt is an expensive element. Higher levels reduce cost effectiveness too much.
    [000129] If necessary, the alloy can also contain Zr, in order to improve resistance to high temperature and resistance to oxidation. The upper limit is set at 0.20% Zr for cost reasons, since Zr is a rare element.
    [000130] If necessary, boron can be added to the alloy, as boron improves creep resistance. Therefore, a content of at least 0.0001% should be present. At the same time, this surfactant element prevents resistance to oxidation. Therefore, a maximum of 0.008% of boron is established.
    [000131] Nickel stabilizes the austenitic matrix and is necessary to form the Y 'phase, which contributes to heat resistance / creep resistance. In the case of a nickel content below 35%, the heat resistance / creep resistance is reduced too much, which is why 35% is the lower limit.
    [000132] The following relationship between Cr, Fe and Co must be satisfied so that, as explained in the examples, sufficient wear resistance is given: Cr + Fe + Co> 25% (1) with Cr, Fe and Co are the concentration of the respective elements in% by mass.
    [000133] In addition, the following relationship must be satisfied, in order to provide sufficient 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) where Ti, Al, Fe, Co, Cr and C are the concentration of the respective elements in mass% and fh is expressed in %. The limits for fh were detailed in detail in the preceding text.
    [000134] If necessary, resistance to oxidation can be further improved with additives of elements with an affinity for oxygen, such as yttrium, marsh, cerium, hafnium. This occurs, in which these are incorporated into the oxide layer and there block the oxygen diffusion path at the grain boundaries.
    [000135] The upper limit of yttrium is set at 0.20% for reasons of cost, since yttrium is a rare element.
    [000136] The upper limit of lanthanum is set at 0.20% for reasons of cost, since yttrium is a rare element.
    [000137] The upper limit of cerium is set at 0.20% for reasons of cost, since yttrium is a rare element.
    [000138] Instead of Ce or La, the mixed metal Cer can also be used. The upper limit of the mixed metal Cer is set at 0.20% for cost reasons.
    [000139] The upper limit of hafnium is set at 0.20% for reasons of cost, since yttrium is a rare element.
    [000140] If necessary, the alloy may also contain tantalum, since tantalum also increases resistance to high temperature, promoting the formation of the Y 'phase. Higher levels increase costs considerably, since tantalum is a rare element. Therefore, the upper limit is set at 0.60%.
    [000141] Pb is limited to a maximum of 0.002%, as this element reduces resistance to oxidation and resistance to high temperature. The same applies to Zn and Sn.
    [000142] In addition, the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb must be satisfied in order to provide 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), with Cr, Mo, W, Fe, Co, Ti, Al and Nb being the concentration of the respective elements in% by mass and fver is expressed in%. The limits for fh were detailed in detail in the preceding text.













    List of reference numbers
    [000143] Figure 1: Volume loss of the NiCr20TiAl pin load 320776 according to the current state of the art as a function of the test temperature measured with 20 N, 1 mm path, 20 Hz and with the dynamometric module (a). The tests at 25 and 300oC were carried out for 1 hour and the tests at 600 and 800oC were carried out for 10 hours.
    [000144] Figure 2: Volume loss of NiCr20TiAl pin load 320776 according to the current state of the art and stelite cast alloy 6 as a function of the test temperature measured with 20 N, 1 mm path, 20 Hz and with the dynamometric module (n). The tests at 25 and 300oC were carried out for 1 hour and the tests at 600 and 800oC were carried out for 10 hours.
    [000145] Figure 3: Loss of volume of the NiCr20TiAl pin load 320776 according to the current state of the art as a function of the test temperature measured with 20 N, 1 mm path, 20 Hz and with the dynamometric module (n). The tests at 25 and 300oC were carried out for 1 hour and the tests at 600 and 800oC were carried out for 10 hours. In addition, a test was carried out at 800oC with 20 N for 2 hours + 100 N for 5 hours.
    [000146] Figure 4: Loss of pin volume for various alloys in table 7 at 25oC, measured with 20 N, 1 mm path, 20 Hz after 1 hour with dynamometric module (a) and (n).
    [000147] Figure 5: Pin volume loss for alloys with different carbon content in table 7, compared to NiCr20TiAl load 320776 at 25oC, measured at 20 N, 1 mm path, 20 Hz with dynamometric module (a) after 10 hours.
    [000148] Figure 6: Loss of pin volume for various alloys in table 7 at 300oC measured with 20 N, 1 mm path, 20 Hz with dynamometric module (a) and (n) after 1 hour.
    [000149] Figure 7: Loss of pin volume for various alloys in table 7 at 600oC measured with 20 N, 1 mm path, 20 Hz after 10 hours with dynamometric module (a) and (n).
    [000150] Figure 8: Loss of pin volume for various alloys in table 7 at 800oC measured with 20 N for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz path and with a dynamometric module ( n).
    [000151] Figure 9: Loss of pin volume for various alloys in table 7 at 800oC measured with 20 N for 2 hours, followed by 100 N for 3 hours, all with a 1 mm, 20 Hz path and with a dynamometric module ( n) together with the sum Cr + Fe + Co of formula (1).
    [000152] Figure 10: Elastic limit Rp0.2 and tensile strength Rm for the alloys in table 8 at 600oC (L: cast on laboratory scale, G: cast on industrial scale).
    [000153] Figure 11: Elastic limit Rp0.2 and tensile strength Rm for the alloys in table 8 at 800oC (L: cast on laboratory scale, G: cast on industrial scale).
    [000154] Figure 12: Elasticity limit Rp0.2 and fh calculated according to formula 2 for the alloys in table 8 at 800oC (L: cast on laboratory scale, G: cast on industrial scale).
    [000155] Figure 13: Proportions of the quantity of the phases in thermodynamic equilibrium as a function of the NiCr20TiAl temperature in the example of load 321426 according to the current state of the art, from tables 5a and 5 b.
    权利要求:
    Claims (11)
    [0001]
    1. Forging nickel-chromium-iron-titanium-aluminum hardening alloy, which has excellent wear resistance, and, at the same time, high creep resistance, good resistance to high temperature corrosion and good processability, the referred alloy being characterized because it comprises (% by mass): 18 to 26% Cr, 1.5 to 3.0% Ti, 0.6 to 2.0% Al, 8.0 to 20% Fe, 0.04 to 0 , 10% C, 0.0005 to 0.050% N, 0.0005 to 0.030% P, max. 0.010% S, max. 0.020% O, max. 0.70% Si, max. 2.0% Mn, max. 0.05% Mg, max. 0.05% Ca, <0.05% Mo, <0.05% W, max. 0.05% Nb, <0.015% Cu, max. 0.5% V, 0.001 to 0.02% Ta, more than 0.0 to 7.0% Co, 0.01 to 0.20% Zr, 0.0001 to 0.008% B, optionally the following elements can be 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 the remainder being Ni and unavoidable conventional impurities in contents of: max. 0.002% Pb, max. 0.002% Zn, max. 0.002% Sn, where the nickel content is greater than 50%, and the following ratios must be satisfied: Cr + Fe + Co> 25% (1) 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) with Ti, Al, Fe, Co, Cr and C being the concentration of the elements in mass%, and where fh is expressed in%; and in which the following relationship between Cr, Mo, W, Fe, Co, Ti, Al and Nb is satisfied so that such processability is achieved: 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) with Cr, Mo, W, Fe, Co, Ti, Al and Nb being the concentration of the respective elements in% by mass, and where fver is expressed in%.
    [0002]
    2. Alloy according to claim 1, characterized by the fact that it comprises an Al content of 0.9 to 2.0%.
    [0003]
    3. Alloy according to claim 1 or 2, characterized by the fact that it comprises a C content of 0.01 to 0.10%.
    [0004]
    Alloy according to any one of claims 1 to 4, characterized in that it comprises a B content of 0.0005 to 0.006%.
    [0005]
    Alloy according to any one of claims 1 to 4, characterized by the fact that the Ni content is greater than 45%.
    [0006]
    6. Alloy according to any one of claims 1 to 5, characterized by the fact that the Ni content is greater than 50%.
    [0007]
    7. Alloy, according to any one of claims 1 to 6, characterized by the fact that it presents: Cr + Fe + Co> 26% (1a), with Cr, Fe and Co being the concentration of the respective elements in% in pasta.
    [0008]
    8. Alloy according to any one of claims 1 to 7, 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 respective elements in mass%, and where fh is expressed in%.
    [0009]
    9. Use of the alloy, as defined in any of claims 1 to 8, characterized by the fact that it is like strip, plate, wire, bar, welded pipe with longitudinal seam and seamless pipe.
    [0010]
    10. Use of the alloy, as defined in any one of claims 1 to 8, characterized by the fact that it is for valves, in particular, discharge valves for combustion engines.
    [0011]
    11. Use of the alloy as defined in any one of claims 1 to 8, characterized by the fact that it is as components of gas turbines, as a fixing pin, in springs, in turbochargers.
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    同族专利:
    公开号 | 公开日
    DE102014001328A1|2015-08-06|
    JP2017508075A|2017-03-23|
    JP6370391B2|2018-08-08|
    DE102014001328B4|2016-04-21|
    WO2015117584A1|2015-08-13|
    BR112016011060A2|2017-09-12|
    CN107041147A|2017-08-11|
    EP3102711B1|2018-10-31|
    SI3102711T1|2019-03-29|
    KR20160134647A|2016-11-23|
    US20160289807A1|2016-10-06|
    KR101876399B1|2018-07-09|
    EP3102711A1|2016-12-14|
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    法律状态:
    2017-09-19| B15I| Others concerning applications: loss of priority|
    2017-10-03| B152| Others concerning applications: decision cancelled|
    2018-05-02| 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| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2020-12-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-01-26| B16A| Patent or certificate of addition of invention granted|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
    DE102014001328.6A|DE102014001328B4|2014-02-04|2014-02-04|Curing nickel-chromium-iron-titanium-aluminum alloy with good wear resistance, creep resistance, corrosion resistance and processability|
    DE102014001328.6|2014-02-04|
    PCT/DE2015/000008|WO2015117584A1|2014-02-04|2015-01-12|Hardening nickel-chromium-iron-titanium-aluminium alloy with good wear resistance, creep strength, corrosion resistance and processability|
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