EP4438754A1 - Niobium-cobalt intermetallic alloy useful for high temperature applications - Google Patents
Niobium-cobalt intermetallic alloy useful for high temperature applications Download PDFInfo
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- EP4438754A1 EP4438754A1 EP24164207.3A EP24164207A EP4438754A1 EP 4438754 A1 EP4438754 A1 EP 4438754A1 EP 24164207 A EP24164207 A EP 24164207A EP 4438754 A1 EP4438754 A1 EP 4438754A1
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- European Patent Office
- Prior art keywords
- alloy
- jonesite
- cobalt
- intermetallic
- niobium
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- BDMHSCBWXVUPAH-UHFFFAOYSA-N cobalt niobium Chemical compound [Co].[Nb] BDMHSCBWXVUPAH-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000001995 intermetallic alloy Substances 0.000 title claims abstract description 18
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 66
- 239000000956 alloy Substances 0.000 claims abstract description 66
- 239000010955 niobium Substances 0.000 claims abstract description 62
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 41
- 229910052742 iron Inorganic materials 0.000 claims abstract description 40
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 38
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 37
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 8
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 8
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 239000011651 chromium Substances 0.000 description 40
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 34
- 239000012071 phase Substances 0.000 description 26
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 239000011572 manganese Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000002485 combustion reaction Methods 0.000 description 8
- 238000013461 design Methods 0.000 description 7
- 230000005496 eutectics Effects 0.000 description 7
- 238000007792 addition Methods 0.000 description 6
- 230000006399 behavior Effects 0.000 description 6
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 6
- 239000003345 natural gas Substances 0.000 description 6
- 238000010587 phase diagram Methods 0.000 description 6
- 238000005496 tempering Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 238000005275 alloying Methods 0.000 description 5
- 238000007571 dilatometry Methods 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 238000011835 investigation Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910000604 Ferrochrome Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 229910020598 Co Fe Inorganic materials 0.000 description 2
- 229910017061 Fe Co Inorganic materials 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910000601 superalloy Inorganic materials 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- VSZWPYCFIRKVQL-UHFFFAOYSA-N selanylidenegallium;selenium Chemical compound [Se].[Se]=[Ga].[Se]=[Ga] VSZWPYCFIRKVQL-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
Definitions
- the invention relates to niobium-cobalt (Nb-Co) alloys having a microstructure useful for high-temperature applications in the fields of aerospace and combustion engine technology.
- Hydrogen propulsion concept for powering aircraft may enable the aviation industry to achieve net zero CO 2 emission goals in the near future.
- Hydrogen internal combustion engine ICE is one of the approaches to substantially reduce combustion emission compared to diesel/natural gas engine for on-road and off-road application.
- ICE Hydrogen internal combustion engine
- To adopt hydrogen fuel for jet or ICE application different combustion behaviors are expected compared to kerosene fuel for jet engine and diesel/natural gas fuel for ICE.
- new alloy/material with good corrosion and hot corrosion resistance along with high temperature strength is needed for making some of the engine components.
- Diesel engines built according to the new designs use higher combustion pressures, higher operating temperatures and less lubrication than previous designs.
- Components of the new designs, including valve seat inserts (VSI) have experienced significantly higher wear rates.
- Exhaust and intake valve seat inserts and valves, for example, must be able to withstand a high number of valve impact events and combustion events with minimal wear (e.g., abrasive, adhesive and corrosive wear). This has motivated a shift in materials selection toward materials that offer improved wear resistance relative to the valve seat insert materials that have traditionally been used by the diesel and natural gas engine industry.
- a cobalt-niobium intermetallic alloy comprises, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements.
- a cobalt-niobium intermetallic alloy consists essentially of, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements.
- a cobalt-niobium intermetallic alloy consists of, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements.
- the alloy includes at least 5 wt.% Cr, at least 0.1 wt.% Fe, at least 0.01 wt.% Ni and/or at least 0.5 wt.% Si;
- the alloy includes at least 5 wt.% Cr, at least 0.01 wt.% Ni, at least 0.1 wt.% Fe and at least 0.5 wt.% Si;
- the alloy includes up to 1.5 wt.% total of other elements including up to 0.25 wt.% C, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.1 wt.% P, up to 0.1 wt.% S, up to 0.15 wt.% N, up to 0.1 wt.% V, up to 0.1 wt.% Ti, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1
- the alloy includes B in an amount of 0.001 to 0.05 wt.% B; (e) the alloy includes 0.01 to 0.25 wt.% C, 0.01 to 0.1 wt.% Mn, 1 to 3 wt.% Si, 0.01 to 5 wt.% Ni, 5 to 8.5 wt.% Cr, 0.01 to 0.2% Mo, 35 to 80 wt.% Co, 0.1 to 6 wt.% Fe, and 10 to 45 wt.% Nb; (f) the alloy has a cast structure in which an intradendritic region includes Nb 6 Co 7 and/or NbCo 2 intermetallic phases; (g) the alloy has a cast structure in which an interdendritic region includes a mixture of Nb 6 Co 7 and NbCo 2 intermetallic phases; (h) the alloy has a cast structure of only the Nb 6 Co 7 intermetallic phase; (i) the alloy has a cast structure of only the NbCo 2 intermetallic phase; (j)
- a cobalt-niobium alloy system (referred to herein as Jonesite 21) can be characterized as a fully intermetallic phase superalloy for high temperature aerospace or automotive applications such as gas turbine, jet engine, and internal combustion (IC) engine valve train component applications such as valve seat insert (VSI) applications.
- IC internal combustion
- VSI valve seat insert
- a general alloy design concept for Jonesite 21 is an alloy composition which can be solidified into Nb 6 Co 7 and/or NbCo 2 phases as illustrated with the binary phase diagram of Nb and Co shown in Figure 1 .
- Jonesite 21 can include one or more intermetallic phases depending on the ratio of cobalt (Co) to niobium (Nb).
- a casting of Jonesite 21 can have a microstructure with 100 vol.% of Nb 6 Co 7 or 100 vol.% of NbCo 2 or various ratios of these two intermetallic phases depending on the Co and Nb contents.
- chromium (Cr), iron (Fe), nickel (Ni) and/or silicon (Si) can be included in the alloy system as alloying elements to control the size and distribution of solidification substructure in Jonesite 21.
- Nb-Co binary phase diagram (in weight percent).
- the compositional range of Jonesite 21 in the binary phase diagram is from 37.4 wt.% Co to 57.4 wt.% Co without considering the other alloying elements (Cr, Si, Fe, Ni, etc.).
- the solidified structure will be 100% Nb 6 Co 7 whereas at 57.4 wt.% Co the solidified structure will be 100% NbCo 2 .
- the solidified structure will be 50 vol.% Nb 6 Co 7 and 50 vol.% of NbCo 2 .
- the solidified structure will be a mixture of Nb 6 Co 7 and NbCo 2 with the amount of Nb 6 Co 7 varying between 100 vol. % to 50 vol. % as the amount of Co increases from 37.4 wt.% to 45.5 wt.%.
- the solidified structure will be a mixture of Nb 6 Co 7 and NbCo 2 with the amount of Nb 6 Co 7 varying between 50 vol. % to 0 vol. % as the amount of Co increases from 45.5 wt.% to 57.4 wt.%.
- the Co to Nb ratio (wt.%) is about 0.83.
- the initial solidification phase can be Nb 6 Co 7 or NbCo 2 .
- the specific alloy should have a Co to Nb ratio (wt.%) between 0.83 to 1.35.
- the specific alloy should have a Co to Nb ratio (wt.%) between 0.6 to 0.83.
- Jonesite 21 has a total Co plus Nb content of at least 70 wt. % and 5 to 30 wt.% total Cr, Ni, Fe and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si. In another embodiment, Jonesite 21 can have a Co to Nb ratio of 0.6 to 1.35.
- Jonesite 21 can include one or more other elements which enhance properties of the alloy.
- such elements include effective amounts of chromium (Cr), silicon (Si), iron (Fe), nickel (Ni), and boron (B).
- Jonesite 21 can be free of intentional additions of other elements such as carbon (C), phosphorus (P), sulfur (S), nitrogen (N), oxygen (O), manganese (Mn), molybdenum (Mo), vanadium (V), aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), and tungsten (W).
- some elements can be present in incidental/impurity total amounts of 1.5 wt.
- ferrochromium typically has a mixture of about 75 wt.% Cr and 25 wt.% Fe.
- Fe would be present in an amount of about 1.25 to 2.5 wt. %.
- Jonesite 21 includes 5 to 30 wt.% total Cr, Si, Fe and/or Ni and less than 1.5 wt.% total C, B, Mn, Mo, P, S, N and other impurities including V, Ti, Al, Hf, Zr, Ta and W.
- Jonesite 21 can include up to 0.25 wt.% C, up to 0.05 wt.% B, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.025 wt.% P, up to 0.025 wt.% S, up to 0.15 wt.% N, up to 0.1 wt.% V, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta and up to 0.1 wt.% W.
- Jonesite 21 can be free of B or include up to 0.05 wt.% B.
- B can be added in an amount effective for grain refinement such as in a range of 0.001 to 0.005 wt.% B or 0.005 to 0.01 wt.% B.
- Jonesite 21 can include Cr in an amount effective to refine the microstructure.
- Cr is added in an amount of 5 to 10 wt.%.
- Cr is added in a range of 5 to 6 wt.% Cr, 6 to 7 wt.% Cr or 7 to 8 wt.% Cr or 8 to 8.5 wt. % Cr.
- Jonesite 21 can include Fe in an amount effective to reduce the cost of the alloy additions.
- Fe is added in an amount of up to 10 wt.%, such as 1 to 6 wt.% Fe.
- Fe can be added in a range of 1 to 2 wt.% Fe, 2 to 3 wt.% Fe, 3 to 4 wt.% Fe, 4 to 5 wt.% Fe or 5 to 5.5 wt.% Fe.
- Jonesite 21 can include Ni in an amount effective to reduce the cost of alloy additions.
- Ni is added in an amount of up to 12 wt.%.
- Ni can be added in a range of 0.01 to 1 wt.% Ni, 1 to 2 wt. % Ni, 2 to 3 wt.% Ni, 3 to 4 wt.% Ni or 4 to 5 wt.% Ni.
- Jonesite 21 can include Si in an amount effective to promote castability.
- Si is added in an amount of up to 3 wt.%.
- Si can be added in a range of 1 to 3 wt.% Si such as 1 to 2 wt.% Si or 2 to 3 wt.% Si.
- Jonesite 21 can include up to 0.25 wt.% C.
- C can be added in a range of 0.01 to 0.15 wt.% C or 0.15 to 0.25 wt.% C.
- Jonesite 21 can include up to 0.1 wt.% Mn.
- Mn can be added in a range of 0.01 to 0.06 wt.% Mn.
- Jonesite 21 can include up to 0.2 wt.% Mo.
- Mo can be added in a range of 0.01 to 0.1 wt.% Mo or 0.1 to 0.2 wt.% Mo.
- Jonesite 21 can include up to 0.15 wt.% N.
- N can be added in a range of 0.01 to 0.1 wt.% N or 0.1 to 0.15 wt.% N.
- Jonesite 21 can include up to 0.1 wt.% Al.
- Al can be added in a range of 0.001 to 0.1 wt.% Al.
- Jonesite 21 can include incidental amounts of refractory elements V, Ti, Hf, Zr, Ta and W in a total amount of up to 0.1 wt. % each.
- Jonesite 21 can include up to 0.1 wt.% V, up to 0.1 wt.% Ti, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta and up to 0.1 wt.% W.
- compositions of Jonesite 21 are set forth in Table 1.
- Table 1 Compositions of Jonesite 21 Heats Heat C Mn Si Ni Cr Mo Co Fe Nb B N 9G27XA 0.240 0.040 2.15 0.10 8.10 0.070 59.57 5.19 25.13 - 9G30XA 0.015 0.010 1.94 0.03 8.20 0.042 69.4 0.11 20.92 0.0086 0.131 9H03XA 0.016 0.010 1.10 0.05 8.04 0.060 71.8 0.10 18.50 0.0084 0.110 9H11XA 0.027 0.058 2.60 0.23 8.26 0.170 76.4 0.70 11.56 0.0053 - 2K16XA 0.063 0.031 2.01 2.01 6.17 0.024 57.80 3.97 27.56 0.046 2K29XA 0.075 0.038 1.98 2.52 6.19 0.025 56.80 4.17 26.69 0.062 2K30XA 0.108 0.041 2.16 4.11 5.35 0.028 53.10 4.66
- the Jonesite 21 alloys have incidental amounts of other elements including phosphorus (P) and sulfur (S) with a maximum of 0.025% P and a maximum of 0.025% S.
- Jonesite 21 Properties of Jonesite 21 are compared to two other LE Jones alloys called Jonesite 19 and J513.
- alloy heats 9H20XA, 2D27XA, 2J12XA and 9H26XA correspond to Jonesite 19
- alloy heat 9K19XA corresponds to J513. Table 2.
- the Jonesite 19 and J513 alloys have incidental amounts of other elements including phosphorus (P) and sulfur (S) with a maximum of 0.025% P and a maximum of 0.025% S.
- Figures 2A , 2B and 2C show a general microstructure and microstructural distribution in Jonesite 21 under 200X, 1000X, and 3000X magnification backscattered electron images, respectively. It is clearly shown that under normal casting solidification conditions, the intermetallic phases exhibited very uniform distribution, at large, in cellular dendritic morphology. In the interdendritic regions, finer lamella eutectic phases of Nb 6 Co 7 and NbCo 2 can be identified.
- Figure 3 shows an SEM image marked with three locations where EDS analysis was performed representing matrix intermetallic phase (spot 1 - intradendritic region), interdendritic region with lamella eutectic phases (spot 2 - intradendritic region), and darker particle phase (spot 3 - dark particle in interdendritic region).
- the detailed EDS analysis results for the three spots can be found in Figures 4 , 5 and 6 , respectively.
- the % of each intermetallic phase can be estimated.
- the alloy contains approximately 52 at.% of Nb 6 Co 7 and 48 at.% of fully eutectic (56.8 at.% Co) phases.
- the fully eutectic phases contain,
- / (67 at.%-49.5 at.%) 0.583, approximately 58 at.% of Nb 6 Co 7 and 42 at.% of NbCo 2 .
- the alloy can have a mixture of about 79.9 at.% of Nb 6 Co 7 and about 20.1 at.% of NbCo 2 .
- Figure 7 shows elemental dot mapping in Jonesite 21 showing major alloying elemental distribution primarily related to three phases namely, Nb-Co intermetallic, Co-Nb intermetallic and Co-Cr-Nb phase.
- Figure 8 is a graph of hot hardness comparing Jonesite 21 to other LE Jones alloys Jonesite 19 and J513.
- Hot hardness values for measurements at various temperatures are set forth in the following Table 3 in which sample heat 2K29XA corresponds to Jonesite 21, sample heat 2D27XA corresponds to Jonesite 19 and sample heat 9K19XA corresponds to J513.
- Table 3 Hot Hardness Test Data Temperature °F HV10 HV10 HV10 Jonesite 21 Jonesite 19 J513 70 765 550 721 200 720 541 702 400 633 504 672 600 662 496 610 800 644 472 597 1000 598 469 527 1200 570 452 356 1400 455 365 208
- the hardness data from Table 4 is illustrated in the graph of hardness versus tempering temperature shown in Figure 10 and the radial crush data is illustrated in the graph of compressive yield strength (CYS) versus tempering temperature shown in Figure 11 .
- the heats tested are 2K16XA (data points shown as circles), 2K29XA (data points shown as diamonds) and 3B22XA (data points shown as triangles).
- the alloys tested were hardened at 1700 °F and tempered for 3 hours. Sustainable bulk hardness was exhibited in Jonesite 21 from ambient to greater than 800°C. There was a general trend that an increase in tempering temperature increased the radial crush toughness within a range from ambient through 816°C.
- Thermal conductivity data is listed below in Table 5 and illustrated in the graph shown in Figure 12 in which Jonesite 21 corresponds to heats 9H11XA and 2K29XA and Jonesite 19 corresponds to heats 9H26XA and 2J12XA.
- Table 5 Thermal Conductivity (W/m-K) Data Temperature °F 9H11XA 2K29XA 9H26XA 2J12XA 25 11.3 8.3 9.8 9.3 100 13.1 8.6 10.9 10.2 200 14.9 10.3 12.3 12.1 300 16.6 11.5 13.8 13.3 400 18.2 13.1 15.4 14.5 500 20 13.8 17 15.8 600 21.5 17.2 18.8 19.4 700 23.5 18.4 21.3 21 800 19.5 22.3 900 21.2 24.1 1000 22.9 26
- Thermal conductivity data of Jonesite 21 shows the influence of Nb to Co ratio.
- the thermal conductivity data shows lower thermal conductivity for alloys with a higher Nb: Co ratio.
- Low thermal conductivity of Jonesite 21 at lower temperature can be beneficial to some engineering applications; for instance, potential application as surface coating material for hydrogen storage or transportation equipment.
- HBJ(60) hardness measurement is a bulk hardness scale testing method. Not like a microhardness test such as Vickers hardness, HBJ hardness has, at large, a good correlation with compressive yield strength for metals and alloys.
- the hardness indenter applied for HBJ(60) is 1/8" spherical in shape and made of aluminum oxide type ceramic material. Compared to Vickers hardness that the indenter is made of diamond, a higher maximum testing temperature can be applied for HBJ(60) testing method than Vickers hardness.
- Figure 13 is a graph showing a bulk hardness comparison among Jonesite 21, Jonesite 19, and J513.
- the heat composition of Jonesite 21, Jonesite 19 and J513 adopted for the comparative study can be summarized in Table 6.
- the hardness range measured within a temperature range from ambient to 900°C.
- J513 possessed higher bulk hardness than Jonesite 21 and Jonesite 19.
- the test temperature was greater than 500°C, the bulk hardness of J513 was lower than Jonesite 21 and Jonesite 19.
- the testing results have manifested that Jonesite 19 and Jonesite 21 possess a higher elevated temperature capability than J513. Table 6.
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- Powder Metallurgy (AREA)
Abstract
A cobalt-niobium intermetallic alloy comprising, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements including up to 0.25 wt.% C, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.1 wt.% P, up to 0.1 wt.% S, up to 0.15 wt.% N, up to 0.1 wt.% V, up to 0.1 wt.% Ti, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta, up to 0.1 wt.% W and up to 0.05 wt.% B. The alloy can have a cast structure in which an intradendritic region includes Nb6Co7 and/or NbCo2 intermetallic phases and/or a cast structure in which an interdendritic region includes a mixture of Nb6Co7 and NbCo2 intermetallic phases.
Description
- The invention relates to niobium-cobalt (Nb-Co) alloys having a microstructure useful for high-temperature applications in the fields of aerospace and combustion engine technology.
- More restrictive exhaust emissions laws for both jet and diesel/natural gas engines have driven changes in engine designs. For jet engine application, one of the approaches to meet the emission regulations is to continue the development of advanced gas turbine propulsion technologies and improve jet engine efficiency. For diesel/natural gas engines the new design includes the need for high-pressure electronic fuel injection systems. Higher temperature and pressure working condition is involved in new jet and diesel/natural gas engine designs.
- Hydrogen propulsion concept for powering aircraft may enable the aviation industry to achieve net zero CO2 emission goals in the near future. Hydrogen internal combustion engine (ICE) is one of the approaches to substantially reduce combustion emission compared to diesel/natural gas engine for on-road and off-road application. To adopt hydrogen fuel for jet or ICE application, different combustion behaviors are expected compared to kerosene fuel for jet engine and diesel/natural gas fuel for ICE. To ensure hydrogen fuel jet engine and ICE to achieve designed performance, new alloy/material with good corrosion and hot corrosion resistance along with high temperature strength is needed for making some of the engine components.
- Diesel engines built according to the new designs use higher combustion pressures, higher operating temperatures and less lubrication than previous designs. Components of the new designs, including valve seat inserts (VSI), have experienced significantly higher wear rates. Exhaust and intake valve seat inserts and valves, for example, must be able to withstand a high number of valve impact events and combustion events with minimal wear (e.g., abrasive, adhesive and corrosive wear). This has motivated a shift in materials selection toward materials that offer improved wear resistance relative to the valve seat insert materials that have traditionally been used by the diesel and natural gas engine industry.
- Various investigations have been made in the past with the goal of improving the high-temperature performance of superalloy compositions.
- In view of the service conditions for aerospace/engine parts exposed to high temperature environments, there is a need for alloys having better hot temperature corrosion, abrasive wear and/or impact resistance.
- In an embodiment, a cobalt-niobium intermetallic alloy comprises, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements. In an embodiment, a cobalt-niobium intermetallic alloy consists essentially of, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements. In an embodiment, a cobalt-niobium intermetallic alloy consists of, in weight percent, 35 to 80 wt.% Co, 10 to 45 wt.%, Nb, a total of at least 70 wt.% Co plus Nb, a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si, balance up to 1.5 wt.% total other elements.
- According to various exemplary embodiments, (a) the alloy includes at least 5 wt.% Cr, at least 0.1 wt.% Fe, at least 0.01 wt.% Ni and/or at least 0.5 wt.% Si; (b) the alloy includes at least 5 wt.% Cr, at least 0.01 wt.% Ni, at least 0.1 wt.% Fe and at least 0.5 wt.% Si; (c) the alloy includes up to 1.5 wt.% total of other elements including up to 0.25 wt.% C, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.1 wt.% P, up to 0.1 wt.% S, up to 0.15 wt.% N, up to 0.1 wt.% V, up to 0.1 wt.% Ti, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta, up to 0.1 wt.% W and up to 0.05 wt. % B; (d) the alloy includes B in an amount of 0.001 to 0.05 wt.% B; (e) the alloy includes 0.01 to 0.25 wt.% C, 0.01 to 0.1 wt.% Mn, 1 to 3 wt.% Si, 0.01 to 5 wt.% Ni, 5 to 8.5 wt.% Cr, 0.01 to 0.2% Mo, 35 to 80 wt.% Co, 0.1 to 6 wt.% Fe, and 10 to 45 wt.% Nb; (f) the alloy has a cast structure in which an intradendritic region includes Nb6Co7 and/or NbCo2 intermetallic phases; (g) the alloy has a cast structure in which an interdendritic region includes a mixture of Nb6Co7 and NbCo2 intermetallic phases; (h) the alloy has a cast structure of only the Nb6Co7 intermetallic phase; (i) the alloy has a cast structure of only the NbCo2 intermetallic phase; (j) the alloy includes 5 to 10 wt.% Cr, 0.01 to 5 wt.% Ni, 0.1 to 6 wt.% Fe and 1 to 3 wt.% Si; (k) the alloy includes 5 to 10 wt.% Cr and 0.01 to 5 wt.% Ni; (l) the alloy includes 5 to 10 wt.% Cr and 0.1 to 6 wt.% Fe; (m) the alloy includes 5 to 10 wt.% Cr and 1 to 3 wt.% Si; (n) the alloy includes 0.01 to 5 wt.% Ni and 0.1 to 6% Fe; (o) the alloy includes 0.01 to 5 wt.% Ni and 1 to 3 wt.% Si; (p) the alloy includes 0.1 to 6 wt.% Fe and 1 to 3 wt.% Si; (q); the alloy can be an engine part such as a valve seat insert useful in an internal combustion engine or an aerospace engine part; (r) the alloy has been melted and cast; and/or (s) the valve seat insert includes 0.01 to 0.25 wt.% C, 0.01 to 0.1 wt.% Mn, 1 to 3 wt.% Si, 0.01 to 5 wt.% Ni, 5 to 8.5 wt.% Cr, 0.01 to 0.2 wt.% Mo, 35 to 80 wt.% Co, 0.01 to 6 wt.% Fe, and 10 to 45 wt.% Nb, balance up to 1.5 wt.% total any other elements.
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Figure 1 shows a Nb - Co binary phase diagram. -
Figure 2A shows a back-scattered electron SEM image of Jonesite 21 (Heat 2K16XA) under 200X magnification. -
Figure 2B shows a back-scattered electron SEM image of Jonesite 21 (Heat 2K16XA) under 1000X magnification. -
Figure 2C shows a back-scattered electron SEM image of Jonesite 21 (Heat 2K16XA) under 3000X magnification. -
Figure 3 shows a back-scattered electron SEM image ofJonesite 21 in which EDS analysis is compared at three spots. -
Figure 4 shows EDS analysis for thespot 1 location wherein the intradendritic phase is identified as Nb-Co (29.0 wt.% - 50.5 wt.%) intermetallic phase. -
Figure 5 shows EDS analysis for thespot 2 location wherein the interdendritic region is rich in Co-Nb (55.8 wt.% - 23.5 wt.%) intermetallic phase. -
Figure 6 shows EDS analysis for the spot 3 location wherein the darker particles are rich in Co, Cr, and Nb. -
Figure 7 shows elemental dot mapping inJonesite 21 showing major alloying elemental distribution primarily related to three phases namely, Nb-Co intermetallic, Co-Nb intermetallic and Co-Cr-Nb phase. -
Figure 8 is a graph of hot hardness comparing Jonesite 21 to other LE Jones alloys. -
Figure 9 is a graph of hot hardness comparing Jonesite 21 to Jonesite 19. -
Figure 10 is a graph of hardness versus tempering temperature comparing Jonesite 21 to Jonesite 19. -
Figure 11 is a graph of compressive yield strength (CYS) versus tempering temperature comparing Jonesite 21 to Jonesite 19. -
Figure 12 is a graph of thermal conductivity versus temperature comparing Jonesite 21 to Jonesite 19. -
Figure 13 is a graph showing bulk hardness HBJ(60) comparison at various temperatures for Jonesite 21, Jonesite 19 and J513. -
Figure 14 is a graph showing the effect of specimen heating rate on thermal expansion behavior of Alloy Jonesite 21 andFigure 15 is a graph showing the effect of specimen cooling rate on thermal expansion behavior of Alloy Jonesite 21. - A cobalt-niobium alloy system (referred to herein as Jonesite 21) can be characterized as a fully intermetallic phase superalloy for high temperature aerospace or automotive applications such as gas turbine, jet engine, and internal combustion (IC) engine valve train component applications such as valve seat insert (VSI) applications.
- A general alloy design concept for Jonesite 21 is an alloy composition which can be solidified into Nb6Co7 and/or NbCo2 phases as illustrated with the binary phase diagram of Nb and Co shown in
Figure 1 . -
Jonesite 21 can include one or more intermetallic phases depending on the ratio of cobalt (Co) to niobium (Nb). In an embodiment, a casting of Jonesite 21 can have a microstructure with 100 vol.% of Nb6Co7 or 100 vol.% of NbCo2 or various ratios of these two intermetallic phases depending on the Co and Nb contents. In addition, chromium (Cr), iron (Fe), nickel (Ni) and/or silicon (Si) can be included in the alloy system as alloying elements to control the size and distribution of solidification substructure in Jonesite 21. - An embodiment of the Jonesite 21 alloy system can be illustrated with reference to
Figure 1 , Nb-Co binary phase diagram (in weight percent). The compositional range of Jonesite 21 in the binary phase diagram is from 37.4 wt.% Co to 57.4 wt.% Co without considering the other alloying elements (Cr, Si, Fe, Ni, etc.). As shown in the phase diagram, at 37.4 wt. % Co the solidified structure will be 100% Nb6Co7 whereas at 57.4 wt.% Co the solidified structure will be 100% NbCo2. At 45.5 wt.% Co the solidified structure will be 50 vol.% Nb6Co7 and 50 vol.% of NbCo2. For Co contents between 37.4 and 45.5 wt.%, the solidified structure will be a mixture of Nb6Co7 and NbCo2 with the amount of Nb6Co7 varying between 100 vol. % to 50 vol. % as the amount of Co increases from 37.4 wt.% to 45.5 wt.%. Likewise, the solidified structure will be a mixture of Nb6Co7 and NbCo2 with the amount of Nb6Co7 varying between 50 vol. % to 0 vol. % as the amount of Co increases from 45.5 wt.% to 57.4 wt.%. - At the fully eutectic point, cobalt content is 45.5 wt.%. Thus, the Co to Nb ratio (wt.%) is about 0.83. Depending upon whether the Co to Nb ratio is on the left or right side of the fully eutectic point (45.5 wt.% Co), the initial solidification phase can be Nb6Co7 or NbCo2. For example, if more NbCo2 phase is preferred, then the specific alloy should have a Co to Nb ratio (wt.%) between 0.83 to 1.35. Likewise, if more Nb6Co7 phase is preferred, then the specific alloy should have a Co to Nb ratio (wt.%) between 0.6 to 0.83.
- In an embodiment, Jonesite 21 has a total Co plus Nb content of at least 70 wt. % and 5 to 30 wt.% total Cr, Ni, Fe and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si. In another embodiment, Jonesite 21 can have a Co to Nb ratio of 0.6 to 1.35.
- Jonesite 21 can include one or more other elements which enhance properties of the alloy. For example, such elements include effective amounts of chromium (Cr), silicon (Si), iron (Fe), nickel (Ni), and boron (B). In addition, Jonesite 21 can be free of intentional additions of other elements such as carbon (C), phosphorus (P), sulfur (S), nitrogen (N), oxygen (O), manganese (Mn), molybdenum (Mo), vanadium (V), aluminum (Al), titanium (Ti), hafnium (Hf), zirconium (Zr), tantalum (Ta), and tungsten (W). Depending on the purity of alloying elements, some elements can be present in incidental/impurity total amounts of 1.5 wt. % or less. For Nb, Cr, Ni, Fe and Si, it is preferred to use 99%+ pure Nb, Cr, Ni, Fe, and Si additions. However, an addition of ferrochromium can be used as the Cr/Fe addition in which case the ferrochromium typically has a mixture of about 75 wt.% Cr and 25 wt.% Fe. Thus, if ferrochromium is used to provide a Cr content of 5-10 wt.% Cr, Fe would be present in an amount of about 1.25 to 2.5 wt. %.
- In an embodiment,
Jonesite 21 includes 5 to 30 wt.% total Cr, Si, Fe and/or Ni and less than 1.5 wt.% total C, B, Mn, Mo, P, S, N and other impurities including V, Ti, Al, Hf, Zr, Ta and W. For example,Jonesite 21 can include up to 0.25 wt.% C, up to 0.05 wt.% B, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.025 wt.% P, up to 0.025 wt.% S, up to 0.15 wt.% N, up to 0.1 wt.% V, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta and up to 0.1 wt.% W. - In an embodiment,
Jonesite 21 can be free of B or include up to 0.05 wt.% B. In an example, B can be added in an amount effective for grain refinement such as in a range of 0.001 to 0.005 wt.% B or 0.005 to 0.01 wt.% B. - In an embodiment,
Jonesite 21 can include Cr in an amount effective to refine the microstructure. Preferably, Cr is added in an amount of 5 to 10 wt.%. In an example, Cr is added in a range of 5 to 6 wt.% Cr, 6 to 7 wt.% Cr or 7 to 8 wt.% Cr or 8 to 8.5 wt. % Cr. - In an embodiment,
Jonesite 21 can include Fe in an amount effective to reduce the cost of the alloy additions. Preferably, Fe is added in an amount of up to 10 wt.%, such as 1 to 6 wt.% Fe. In an example, Fe can be added in a range of 1 to 2 wt.% Fe, 2 to 3 wt.% Fe, 3 to 4 wt.% Fe, 4 to 5 wt.% Fe or 5 to 5.5 wt.% Fe. - In an embodiment,
Jonesite 21 can include Ni in an amount effective to reduce the cost of alloy additions. Preferably, Ni is added in an amount of up to 12 wt.%. In an example, Ni can be added in a range of 0.01 to 1 wt.% Ni, 1 to 2 wt. % Ni, 2 to 3 wt.% Ni, 3 to 4 wt.% Ni or 4 to 5 wt.% Ni. - In an embodiment,
Jonesite 21 can include Si in an amount effective to promote castability. Preferably, Si is added in an amount of up to 3 wt.%. In an example, Si can be added in a range of 1 to 3 wt.% Si such as 1 to 2 wt.% Si or 2 to 3 wt.% Si. - In an embodiment,
Jonesite 21 can include up to 0.25 wt.% C. In an example, C can be added in a range of 0.01 to 0.15 wt.% C or 0.15 to 0.25 wt.% C. - In an embodiment,
Jonesite 21 can include up to 0.1 wt.% Mn. In an example, Mn can be added in a range of 0.01 to 0.06 wt.% Mn. - In an embodiment,
Jonesite 21 can include up to 0.2 wt.% Mo. In an example, Mo can be added in a range of 0.01 to 0.1 wt.% Mo or 0.1 to 0.2 wt.% Mo. - In an embodiment,
Jonesite 21 can include up to 0.15 wt.% N. In an example, N can be added in a range of 0.01 to 0.1 wt.% N or 0.1 to 0.15 wt.% N. - In an embodiment,
Jonesite 21 can include up to 0.1 wt.% Al. In an example, Al can be added in a range of 0.001 to 0.1 wt.% Al. - In an embodiment,
Jonesite 21 can include incidental amounts of refractory elements V, Ti, Hf, Zr, Ta and W in a total amount of up to 0.1 wt. % each. For example,Jonesite 21 can include up to 0.1 wt.% V, up to 0.1 wt.% Ti, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta and up to 0.1 wt.% W. - Exemplary compositions of
Jonesite 21 are set forth in Table 1.Table 1. Compositions of Jonesite 21 HeatsHeat C Mn Si Ni Cr Mo Co Fe Nb B N 9G27XA 0.240 0.040 2.15 0.10 8.10 0.070 59.57 5.19 25.13 - 9G30XA 0.015 0.010 1.94 0.03 8.20 0.042 69.4 0.11 20.92 0.0086 0.131 9H03XA 0.016 0.010 1.10 0.05 8.04 0.060 71.8 0.10 18.50 0.0084 0.110 9H11XA 0.027 0.058 2.60 0.23 8.26 0.170 76.4 0.70 11.56 0.0053 - 2K16XA 0.063 0.031 2.01 2.01 6.17 0.024 57.80 3.97 27.56 0.046 2K29XA 0.075 0.038 1.98 2.52 6.19 0.025 56.80 4.17 26.69 0.062 2K30XA 0.108 0.041 2.16 4.11 5.35 0.028 53.10 4.66 35.00 0.071 3B22XA 0.102 0.029 1.69 4.63 7.48 0.058 58.2 2.77 24.44 0.115 - In the above Table 1, the
Jonesite 21 alloys have incidental amounts of other elements including phosphorus (P) and sulfur (S) with a maximum of 0.025% P and a maximum of 0.025% S. - Properties of
Jonesite 21 are compared to two other LE Jones alloys calledJonesite 19 and J513. In Table 2, alloy heats 9H20XA, 2D27XA, 2J12XA and 9H26XA correspond to Jonesite 19 and alloy heat 9K19XA corresponds to J513.Table 2. Compositions of Jonesite 19 and J513 HeatsHeat C Mn Si Ni Cr Mo Co Fe Nb B N 9H20XA 0.023 0.007 2.67 66.9 14.8 0.157 0.1 0.05 15.73 0.058 2D27XA 0.241 0.067 1.65 45.43 8.51 1.86 6.31 7.97 26.2 2J12XA 0.001 0.061 1.9 56.2 7.64 0.122 4.36 3.74 24.21 9H26XA 0.028 0.02 3.12 60.4 12.05 0.086 6.01 0.163 >9 9K19XA 1.797 0.435 0.625 0.03 16.16 12.82 21.48 43.9 0.09 - In the above Table 2, the
Jonesite 19 and J513 alloys have incidental amounts of other elements including phosphorus (P) and sulfur (S) with a maximum of 0.025% P and a maximum of 0.025% S. -
Figures 2A ,2B and 2C show a general microstructure and microstructural distribution inJonesite 21 under 200X, 1000X, and 3000X magnification backscattered electron images, respectively. It is clearly shown that under normal casting solidification conditions, the intermetallic phases exhibited very uniform distribution, at large, in cellular dendritic morphology. In the interdendritic regions, finer lamella eutectic phases of Nb6Co7 and NbCo2 can be identified.Figure 3 shows an SEM image marked with three locations where EDS analysis was performed representing matrix intermetallic phase (spot 1 - intradendritic region), interdendritic region with lamella eutectic phases (spot 2 - intradendritic region), and darker particle phase (spot 3 - dark particle in interdendritic region). The detailed EDS analysis results for the three spots can be found inFigures 4 ,5 and 6 , respectively. - For an alloy with a fixed Nb to Co ratio, e.g. 53.0 at.% Co and 47.0 at.% Nb, based on the Nb-Co binary phase diagram and using the lever rule, the % of each intermetallic phase can be estimated. Here, 153.0 at.% -56.8 at.% (eutectic point) | = 3.8 at.%; 3.8 at.%/(56.8 at.%-49.5 at.%)=3.8 at.%/7.3 at.%=0.521. Thus, the alloy contains approximately 52 at.% of Nb6Co7 and 48 at.% of fully eutectic (56.8 at.% Co) phases. The fully eutectic phases contain, |56.8 at.%-67 at.% | / (67 at.%-49.5 at.%) = 0.583, approximately 58 at.% of Nb6Co7 and 42 at.% of NbCo2. Thus, the alloy can have a mixture of about 79.9 at.% of Nb6Co7 and about 20.1 at.% of NbCo2.
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Figure 7 shows elemental dot mapping inJonesite 21 showing major alloying elemental distribution primarily related to three phases namely, Nb-Co intermetallic, Co-Nb intermetallic and Co-Cr-Nb phase. -
Figure 8 is a graph of hothardness comparing Jonesite 21 to other LE Jones alloys Jonesite 19 and J513. Hot hardness values for measurements at various temperatures are set forth in the following Table 3 in which sample heat 2K29XA corresponds to Jonesite 21, sample heat 2D27XA corresponds to Jonesite 19 and sample heat 9K19XA corresponds to J513.Table 3. Hot Hardness Test Data Temperature °F HV10 HV10 HV10 Jonesite 21 Jonesite 19J513 70 765 550 721 200 720 541 702 400 633 504 672 600 662 496 610 800 644 472 597 1000 598 469 527 1200 570 452 356 1400 455 365 208 - As can be seen from the hot hardness data in Table 3,
Jonesite 21 has a higher hot hardness thanJonesite 19 but likeJonesite 19, the hot hardness ofJonesite 21 is sustained at high temperatures compared to J513.Figure 9 is a graph of hot hardness ofJonesite 21 compared toJonesite 19. - In hardness and radial crush tests (8.33 x ft-lbf) versus tempering temperature,
Jonesite 21 heats 2K16XA (#1), 2K29XA (#2) and 3B22XA (#3) were compared and the results are listed below in Table 4.Table 4. Rockwell Hardness (HRC) and Radial Crush Toughness (CYS) Data Temp. °F Temp. °C HRC (#1) HRC (#2) HRC (#3) 8.33 x ft-lbf (#1) 8.33 x ft-lbf (#2) 8.33xft-lbf (#3) 70 21 61.4 61.4 59.4 0.108 0.069 0.1549 800 427 60.8 61.5 59.2 0.112 0.091 0.1541 900 482 61.2 61.5 59.2 0.095 0.091 0.1717 1000 538 60.7 61.6 59.7 0.148 0.108 0.1809 1050 561 61 61.3 59.6 0.151 0.106 0.2174 1100 593 61.2 61.1 59.4 0.141 0.119 0.1948 1150 621 61.3 61.5 59.1 0.112 0.058 0.1782 1200 649 60.8 61.5 59.8 0.118 0.127 0.2172 1250 677 61.1 61.2 59.7 0.156 0.114 0.1528 1300 704 61.4 61.3 59.6 0.156 0.069 0.2026 1350 732 60.7 61.6 59.8 0.167 0.099 0.1841 1400 760 60.8 61.4 59.6 0.150 0.117 0.1445 1450 788 61.4 - 59.6 0.150 - 0.1994 1500 816 60.9 60.8 59.6 0.160 0.064 0.1595 - The hardness data from Table 4 is illustrated in the graph of hardness versus tempering temperature shown in
Figure 10 and the radial crush data is illustrated in the graph of compressive yield strength (CYS) versus tempering temperature shown inFigure 11 . The heats tested are 2K16XA (data points shown as circles), 2K29XA (data points shown as diamonds) and 3B22XA (data points shown as triangles). The alloys tested were hardened at 1700 °F and tempered for 3 hours. Sustainable bulk hardness was exhibited inJonesite 21 from ambient to greater than 800°C. There was a general trend that an increase in tempering temperature increased the radial crush toughness within a range from ambient through 816°C. - Thermal conductivity data is listed below in Table 5 and illustrated in the graph shown in
Figure 12 in whichJonesite 21 corresponds to heats 9H11XA and 2K29XA andJonesite 19 corresponds to heats 9H26XA and 2J12XA.Table 5. Thermal Conductivity (W/m-K) Data Temperature °F 9H11XA 2K29XA 9H26XA 2J12XA 25 11.3 8.3 9.8 9.3 100 13.1 8.6 10.9 10.2 200 14.9 10.3 12.3 12.1 300 16.6 11.5 13.8 13.3 400 18.2 13.1 15.4 14.5 500 20 13.8 17 15.8 600 21.5 17.2 18.8 19.4 700 23.5 18.4 21.3 21 800 19.5 22.3 900 21.2 24.1 1000 22.9 26 - Thermal conductivity data of
Jonesite 21 shows the influence of Nb to Co ratio. For Heat 9H11XA the Nb:Co ratio is 11.56 wt.%/76.4 wt.% = 0.151 and for Heat 2K29XA the Nb:Co ratio is 26.69 wt.%/56.8 wt.% = 0.469. Accordingly, the thermal conductivity data shows lower thermal conductivity for alloys with a higher Nb: Co ratio. Low thermal conductivity ofJonesite 21 at lower temperature can be beneficial to some engineering applications; for instance, potential application as surface coating material for hydrogen storage or transportation equipment. - HBJ(60) hardness measurement is a bulk hardness scale testing method. Not like a microhardness test such as Vickers hardness, HBJ hardness has, at large, a good correlation with compressive yield strength for metals and alloys. The hardness indenter applied for HBJ(60) is 1/8" spherical in shape and made of aluminum oxide type ceramic material. Compared to Vickers hardness that the indenter is made of diamond, a higher maximum testing temperature can be applied for HBJ(60) testing method than Vickers hardness.
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Figure 13 is a graph showing a bulk hardness comparison amongJonesite 21,Jonesite 19, and J513. The heat composition ofJonesite 21,Jonesite 19 and J513 adopted for the comparative study can be summarized in Table 6. The hardness range measured within a temperature range from ambient to 900°C. Evidently, under 500°C, J513 possessed higher bulk hardness thanJonesite 21 andJonesite 19. When the test temperature was greater than 500°C, the bulk hardness of J513 was lower thanJonesite 21 andJonesite 19. The testing results have manifested thatJonesite 19 andJonesite 21 possess a higher elevated temperature capability than J513.Table 6. Alloy Compositions for Bulk Hardness Comparison Alloy Heat Number C Mn Si Ni Cr Mo w Nb B Fe Co Jonesite 21 3J31XA 0.456 0.065 1.86 7.51 7.50 0.020 <0.005 24.98 0.0087 7.33 50.2 Jonesite 19 2J05XA 0.021 0.134 2.30 48.58 9.11 1.390 0.412 21.98 0.0209 10.11 4.47 J513 9C29O 2.010 0.334 0.526 2.02 16.15 12.12 1.460 ~ 0.0473 45.34 19.17 - The thermal expansion behavior (dilatometry investigation) of Jonesite 21 (3E11XA) was conducted using Linseis dilatometer Model L75HS1000C. The test specimen dimension was ¼" in diameter and 1" long. Three specimen heating rates, 1°/min, 3°/min, and 6°/min were applied. It was revealed that thermal expansion coefficient of
Jonesite 21 was very similar to common martensitic type of steels but lower than conventional high temperature nickel- or cobalt- based alloys. - A linear behavior of
Jonesite 21 was observed when heating rate of 1°/min and 3°/min was applied, respectively. Evidently, no bulk solid phase transformation occurred within the temperature range from ambient to 999°C. As the heating temperature rate increased to 6°/min, only a slight change of thermal expansion rate as a function of temperature was observed. The results of the dilatometry investigation are shown inFigure 14 . - A linear behavior of
Jonesite 21 was observed when cooling rate of 1°/min and 3°/min was applied, respectively. Evidently, no bulk solid phase transformation occurred within the temperature range from ambient to 999°C. As the cooling temperature rate increased to 6°/min, only a slight change of thermal expansion rate as a function of temperature was observed. The results of the dilatometry investigation are shown inFigure 15 . The data forFigures 15 and 15 are tabulated in Table 8.Table 7. Heat (3E11A) composition of Jonesite 21 used for dilatometry investigation.Alloy Heat Number C Mn Si Ni Cr Mo w Nb B Fe Co Jonesite 21 3E11X A 0.254 0.162 1.83 4.36 7.32 0.027 <0.005 25.10 0.0141 2.62 58.5 Table 8 Dilatometry Test Results Coefficient of Thermal Expansion CTE(1/°C×10-5) Temperature ° C 1°C/minute 3°C/minute 6°C/ minute 100 1.13 1.11 0.95 200 1.16 1.16 1.14 300 1.20 1.20 1.18 400 1.23 1.23 1.22 500 1.27 1.27 1.25 600 1.32 1.32 1.29 700 1.36 1.36 1.34 800 1.38 1.38 1.37 825 1.39 1.39 1.37 845 1.39 1.39 1.38 900 1.40 1.41 1.41 999 1.42 1.43 1.43 999 1.40 1.41 1.41 900 1.38 1.39 1.39 845 1.37 1.38 1.36 800 1.37 1.37 1.35 700 1.34 1.35 1.33 600 1.30 1.31 1.28 500 1.26 1.26 1.25 400 1.23 1.23 1.21 300 1.20 1.19 1.18 200 1.16 1.16 1.13 100 1.13 1.11 0.95 - It will be appreciated by those skilled in the art that the present invention can be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The presently disclosed embodiments are therefore considered in all respects to be illustrative and not restricted. The scope of the invention is indicated by the appended claims rather than the foregoing description and all changes that come within the meaning and range and equivalence thereof are intended to be embraced therein.
Claims (15)
- A cobalt-niobium intermetallic alloy comprising, in weight percent,35 to 80 wt.% Co and 10 to 45 wt.% Nb with a total of at least 70 wt.% Co plus Nb;a total of 5 to 30 wt.% Cr, Fe, Ni and Si with up to 10 wt.% Cr, up to 10 wt.% Fe, up to 12 wt.% Ni and up to 3 wt.% Si; andbalance up to 1.5 wt.% total of other elements.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy includes at least 5 wt.% Cr, at least 0.1 wt.% Fe, at least 0.01 wt.% Ni and/or at least 0.5 wt.% Si.
- The cobalt-niobium intermetallic alloy of claim 2, wherein the alloy includes at least 5 wt.% Cr, at least 0.1 wt.% Fe, at least 0.01 wt.% Ni and at least 0.5 wt.% Si.
- The cobalt-base niobium intermetallic alloy of claim 1, wherein the 1.5 wt.% total of other elements includes up to 0.25 wt.% C, up to 0.1 wt.% Mn, up to 0.2 wt.% Mo, up to 0.1 wt.% P, up to 0.1 wt.% S, up to 0.15 wt.% N, up to 0.1 wt. % V, up to 0.1 wt.% Ti, up to 0.1 wt.% Al, up to 0.1 wt.% Hf, up to 0.1 wt.% Zr, up to 0.1 wt.% Ta, up to 0.1 wt.% W and up to 0.05 wt.% B.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy includes B in an amount of 0.001 to 0.05 wt.%.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy includes 0.01 to 0.25 wt.% C, 0.01 to 0.1 wt.% Mn, 1 to 3 wt.% Si, 0.01 to 5 wt.% Ni, 5 to 8.5 wt.% Cr, 0.01 to 0.2 wt.% Mo, 35 to 80 wt.% Co, 0.01 to 6 wt.% Fe, and 10 to 45 wt.% Nb.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy has a cast structure in which an intradendritic region includes Nb6Co7 and/or NbCo2 intermetallic phases.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy has a cast structure in which an interdendritic region includes a mixture of Nb6Co7 and NbCo2 intermetallic phases.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy has a cast structure of only Nb6Co7 intermetallic phase.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy has a cast structure of only NbCo2 intermetallic phase.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy includes 5 to 10 wt.% Cr, 0.01 to 5 wt.% Ni, 0.1 to 6 wt.% Fe and 1 to 3 wt.% Si.
- The cobalt-niobium intermetallic alloy of claim 1, wherein the alloy includes 5 to 10wt.% Cr and 0.01 to 5 wt.% Ni, orwherein the alloy includes 5 to 10 wt.% Cr and 0.1 to 6 wt.% Fe, orwherein the alloy includes 5 to 10 wt.% Cr and 1 to 3 wt.% Si, orwherein the alloy includes 0.01 to 5 wt.% Ni and 0.1 to 6 wt.% Fe, orwherein the alloy includes 0.01 to 5 wt.% Ni and 1 to 3 wt. % Si, orwherein the alloy includes 0.1 to 6 wt.% Fe and 1 to 3 wt.% Si.
- An engine part such as a valve seat insert of a vehicle or an aerospace engine part made of the cobalt-niobium intermetallic alloy of claim 1.
- The engine part of claim 13, wherein the alloy has been melted and cast.
- The engine part of claim 14, wherein the alloy includes 0.01 to 0.25 wt.% C, 0.01 to 0.1 wt.% Mn, 1 to 3 wt.% Si, 0.01 to 5 wt.% Ni, 5 to 8.5 wt.% Cr, 0.01 to 0.2 wt.% Mo, 35 to 80 wt.% Co, 0.1 to 6 wt.% Fe, and 10 to 45 wt.% Nb.
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US11525172B1 (en) * | 2021-12-01 | 2022-12-13 | L.E. Jones Company | Nickel-niobium intermetallic alloy useful for valve seat inserts |
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