GB2394959A - Hafnium particle dispersion hardened nickel-chromium-iron alloys - Google Patents
Hafnium particle dispersion hardened nickel-chromium-iron alloys Download PDFInfo
- Publication number
- GB2394959A GB2394959A GB0225648A GB0225648A GB2394959A GB 2394959 A GB2394959 A GB 2394959A GB 0225648 A GB0225648 A GB 0225648A GB 0225648 A GB0225648 A GB 0225648A GB 2394959 A GB2394959 A GB 2394959A
- Authority
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- United Kingdom
- Prior art keywords
- max
- alloy
- hafnium
- chromium
- nickel
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 66
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000002245 particle Substances 0.000 title claims abstract description 44
- 229910000640 Fe alloy Inorganic materials 0.000 title claims abstract description 15
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000006185 dispersion Substances 0.000 title description 11
- 239000000956 alloy Substances 0.000 claims abstract description 90
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 88
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000010936 titanium Substances 0.000 claims abstract description 26
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000155 melt Substances 0.000 claims abstract description 24
- 239000010955 niobium Substances 0.000 claims abstract description 21
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 21
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 20
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 18
- 239000011651 chromium Substances 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 239000012535 impurity Substances 0.000 claims abstract description 12
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910001175 oxide dispersion-strengthened alloy Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 238000001175 rotational moulding Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000007792 addition Methods 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 239000010703 silicon Substances 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 10
- 239000011733 molybdenum Substances 0.000 claims description 10
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 10
- 239000010937 tungsten Substances 0.000 claims description 10
- 239000002893 slag Substances 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 claims 1
- 229910010340 TiFe Inorganic materials 0.000 claims 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 241000588731 Hafnia Species 0.000 description 4
- 229910001293 incoloy Inorganic materials 0.000 description 3
- 150000001247 metal acetylides Chemical class 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000000611 regression analysis Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910005438 FeTi Inorganic materials 0.000 description 1
- -1 Niobium Hafnium Titanium zirconium Cobalt Tungsten Chemical compound 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 101100253356 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) MEF2 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- RAFPTRANICFIFN-UHFFFAOYSA-N [Mo].[Cr].[Ni].[Mn].[Si].[C] Chemical compound [Mo].[Cr].[Ni].[Mn].[Si].[C] RAFPTRANICFIFN-UHFFFAOYSA-N 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 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
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical class [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000004901 spalling Methods 0.000 description 1
- 238000001991 steam methane reforming Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0207—Using a mixture of prealloyed powders or a master alloy
- C22C33/0228—Using a mixture of prealloyed powders or a master alloy comprising other non-metallic compounds or more than 5% of graphite
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
- C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/48—Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
- Glass Compositions (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
An oxide dispersion strengthened nickel-chromium-iron alloy comprising (in % by weight): Ni 15-50%, Cr 20-40%, Hf 0.01-4.5 %, C 0.01-0.5 %, Si 0.01-2.5 %, Mn0-2.5 %, Mo 0-1.0 %, Nb 0-1.7 %, Ti 0-0.5 %, Zr 0-0.5 %, Co 0-2.0 %, W 0-1.0 %, with the balance being Fe and impurities. At least one of niobium, titanium and zirconium are present and at least part of the hafnium exists as oxide particles. Embodiments are also specified where the chromium range is 19-22 % by weight and the cobalt maximum is 2.05 weight %. The alloy may be used for making into tubes by rotational moulding. The alloy is made by adding hafnium particles to a melt held in a ladle before pouring under conditions such that at least part of the hafnium is oxidised in the melt.
Description
GB 2394959 A continuation (52) cont C7D DJB D805 D807 D810D811 D812 D814
D815 D816
D818 D819 D822 D823 D824 D825 D827 D828D829
D831 D834 D835 D836 D838 D839
(56) Docu meets Cited: EP 0384608 A1 EP 0246092 A2
EP 0065812 A1 JP 630259051 A
SU 001763511 A1 US 5328499 A
(58) Field of Search:
INT CL7 C22C
Other: Online: PAJ, WPI
Bigh Temperature Alloys This invention relates to high temperature alloys, and more particularly to an oxide dispersion strengthened 5 nickelchromium-iron alloy having improved creep resistance and oxidation resistance at high temperatures.
Frequently alloy materials for use at high temperatures, for example, alloy tubes used in ethylene pyrolysis and 10 in steam methane reforming, suffer from insufficient creep resistance. The industry continues to look for improved materials and other technologies to enable more efficient ethylene production under increasingly severe pyrolysis/cracking conditions (higher temperatures, 15 shorter residence times, and lower partial pressures of product), leading to increased ethylene yields. Current alloys have specific issues related to their creep performance which causes failure at increasingly high design process temperatures. This is the case currently 20 for both castable alloy tubes and wrought alloy tubes.
An example of a known alloy material is INCOLOY alloy 803 (UNS S 35045), which is an iron-nickel-chromium alloy 25 specifically designed for use in petrochemical, chemical and thermal processing applications. The composition of INCOLOY 803, by weight, is 25%Cr, 35%Ni, 1%Mn, 0.6%Ti, 0. 5%Al, 0.7%Si, 0.07%C and balance Fe. Relatively unsuccessful efforts have been made to improve the 30 properties of this alloy by the addition of further alloying components and also by cladding.
It has been known for about thirty years that alloy creep resistance can be considerably improved by adding a fine 35 dispersion of oxide particles into a metallic matrix,
À Àee.e..e e e e ÀÀ À À
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À À....
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yielding a so-called oxide dispersion strengthened (ODS) alloy. Such alloys show a creep threshold, that is to say, below a certain stress their creep rate is very low.
This behaviour is commonly explained by interracial 5 pinning of the moving dislocations at the oxide particle; Bartsch, M., A. Wasilkowska, A. Czyrska-Filemonowicz and U. Messerschmidt Ma serial s Science Engineering A 272, 152-162 (1999). It has recently been proposed to provide oxide dispersion strengthened clad tubes based on INCOLOY 10 803, but to date no entirely successful commercial product is available (www. oit.doe.gov/imf/factsheets/mtu tubes).
According to the present invention, an improved creep 15 resistant nickelchromium-iron alloy comprises up to about 5% of hafnium-containing particles. The alloy is particularly useful in the production of creep resistant tubes. 20 Also according to the invention, an improved oxide dispersion strengthened nickel-chromium-iron alloy is provided, which comprises up to about 5% of hafnium, with at least part of the hafnium being present as finely dispersed oxidised particles.
In a first aspect, the present invention provides an oxide dispersion strengthened nickel-chromium-iron alloy comprising, by weight: 30 Carbon 0.01 - 0.5% Silicon 0.1 - 2.5% Manganese 0 - 2.5% Nickel 15 - 50% Chromium 20 - 40% 35 Molybdenum 0 - 1.0%
: t;'.t'\:...,:i _t'_i:.'?.;':: ,i. 1,'j'.'.'\..:i'.:.:;' A::.:._.::.:_:. :::: I.':\ A.:'.': At..!:.,';_.:'._::'.':.',._,,'.::.: 9 '..,'J'_:'1'.:'.. !. 'S. I:.:.:.::,:,i À e ee.ÀeHe ÀÀ À À À
À À
ÀÀÀa Àe C. ae..e.e Niobium 0 - 1.7% Titanium 0 - 0.5% Zirconium 0 - 0.5% Cobalt 0 - 2.0% 5 Tungsten 0 - 1.0% Hafnium 0.01 - 4.5% balance iron and incidental impurities, 10 with the proviso that at least one of niobium, titanium and zirconium is present and that at least part of the hainium is present as finely divided oxide particles.
In a second aspect, the present invention provides a 15 method of manufacturing an oxide dispersion strengthened nickel-chromium-iron alloy which comprises adding finely divided hafnium particles to a melt of the alloy before pouring, under conditions such that at least part of the hafnium is converted to oxide in the melt.
Preferred alloys according to the invention include the following compositions, where all percentages are given by weight: Carbon Silicon Manganese Nickel Chromium Molybdenum A 0.3 - 0.5 0.1 - 2. 5 2.5 max 30 40 20 - 30 1.0 max B 0.03 - 0.2 0.1 - 2.5 2.5 max 30 - 40 20 - 30 1.0 max C 0.3 - 0.5 0.1 - 2.5 2.5 max 40 - 50 30 - 40 1.0 max D 0.03 - 0.2 0.1 2.5 2.5 max 40 - 50 30 - 40 1.0 max E 0.30 - 0.5 0.1 - 2.5 2.5 max 19 - 22 24 - 27 1.0 max F 0.03 - 0.2 0.1 - 2.5 2.5 max 30 - 45 19 - 22 1.0 max
:.'.'&.';.'w'\'i'.-:..::i.-l:.-:.';:-.;;...:.. i:.:.:;:.:-'..,,..'::.'Y:.. ;.'.-.'::..'-.::'..;;'..i.;:..L,:_;;.;::,.;.,:.,;.,;:.i; '-;::.:...'._.;. ::..._.::.:.,:;.:i._, À À Àe.eC À @ .ÀÀ À ÀÀ À À
À ÀÀ À. -
ÀeÀ...ee. Àe Niobium Hafnium Titanium zirconium Cobalt Tungsten A 1.7 max 0.025 - 4.5 0.5 max 0.5 max 2.0 max 1.0 max s 1.7 max 0.025 - 4.5 0.5 max 0.5 max 2.0 max 1.0 max C 1.7 max 0.025 - 4.5 0.5 max 0.5 max 2.0 max 1.0 max D 1.7 max 0.025 - 4.5 0.5 max 0.5 max 2.0 max 1.0 max E 1.7 max 0.025 - 4.5 2.0 max 1.0 max F 1.7 max 0.025 - 4.5 0.5 max 0.5 max 2.0 max 1.0 max balance iron and incidental impurities.
The amount of hafnium in the alloy, by weight, is 5 preferably from 0.05 to 3.0%, more preferably from 0.1% to 1.0% and most preferably from 0.2 to 0.5%. Preferably the hafnium is present in the alloy in the form of finely divided oxidised particles having an average particle size of from 50 microns to 0.25 microns, or less, more 10 preferably from 5 microns to 0.25 microns or less.
A particularly preferred alloy composition according to the invention consists essentially of the following components, by weight: Carbon 0.45% Silicon 1.3% Manganese 0.9% Nickel 33.8% 20 Chromium 25.7% Molybdenum 0. 03% Niobium 0.85% Hafnium 0.25% Titanium 0.1% 25 Zirconium 0.01% Cobalt 0. 04% Tungsten 0.01% Iron balance.
i. in 5;j i ti hi " A 9 we'd I;:,;: i: I,..::.:3i;:.::Lv-.i; ^'.;:i.: \':. :.' '.'. in'.
eeÀÀ e ÀcÀ À À À À À ÀÀÀÀ À e Àe À À e À À À e À. Àe eve Àe ece À Àe Incidental impurities in the alloys of the invention can comprise, for example, aluminium, phosphorus, sulphur, vanadium, zinc, arsenic, nitrogen, tin, lead, copper and 5 cerium, up to a total amount of about 1. 0%.
In the method of the invention, it is important to provide conditions in the melt which permit oxidation of the hafnium particles without allowing detrimental 10 reactions which would result in the hafnium being taken up in the slag. The correct oxidising conditions can be achieved by appropriate adjustment or additions of the components, especially silicon, and by ensuring that unwanted contaminants such as aluminium are absent or 15 kept to a minimum. If the slag is able to react with the oxidised hafnium particles this of course removes them detrimentally from the melt. The level of oxygen in the melt can be varied by micro-additions of, for example, one or more of silicon, niobium, titanium and zirconium, 20 and the optimum free oxygen level necessary to react with the hafnium particles can readily be found by routine experimentation. After the reaction of the hafnium particles with free 25 oxygen, alloying amounts of titanium and/or zirconium may be added, up to the specified limits of 0.5% by weight.
The substantial removal of available free oxygen from the melt helps to ensure that any such titanium and zirconium additions do not form oxides, which could react 30 detrimentally with the hafnium particles and reduce the yields of titanium, zirconium and hafnium present in the alloy. It is important that the hafnium is added to the melt as 35 finely divided particles and that it is oxidised in situ.
3."' 'i:;;::.'.'i "I:'.:.i': '..;;:.';... ':::.":.:'.::: ?. '::.:.:-_::.:; qS.: ';:.; 3:.:.' i_.;.;;_. '.;:::.::'::;::_.:.::.::.:; i':::\;::: ÀÀÀÀ À
e. À. , À À À À
À À À
À Àe e Attempts to \ add large pieces of hafnium to nickel/chromium \micro-alloys have revealed that the hafnium does not perse, but settles to the bottom of the alloy melt, or Reacts with carbon resulting in a 5 decrease of the alloy properties. Surprisingly, we have also found that the addition of hafnia (hafoium oxide) particles directly to the melt does not provide the desired dispersion strengthening either. Hafnia added in this way simply goes into the slag. According to the 10 invention it has been found that it is necessary to carry out the oxidation of the hainium particles in the melt in order to obtain the desired improvement.
The charge make up can be a virgin charge (pure metals), 15 a mixture of virgin charge and reverts, a mixture of virgin charge and ingots, or a mixture of virgin charge and reverts and ingots. The ingots can be made from argon/oxygen decarburisation (AOD) revert alloy treatment or from inhouse reverts treated by argon purging. In 20 each case the chemical composition of the melt should be carefully monitored to avoid contaminants and the formation of unwanted slag. Special care should be taken to deslag the bath, and the maximum amount of slag is preferably removed from the surface of the bath. It is 25 possible to improve slag removal by the use of a neutral deslag powder. If desired the melt can be maintained in an argon atmosphere, but this is not essential.
The melt temperature is preferably in the range of from 30 1580 C to 1700 C, preferably from 1610 C to 1670 C.
Hafnium particles are preferably added to the melt just before pouring the molten alloy into the mould. If a ladle is used, the hafoium is preferably added in the
:..!: G:.:..:'..':';..:!.:.':..:''.i...::'..'.':'.. {.'.':::2'::.::.'..::...::!.......;'::.:.'.'..'. A:::'::::...:..:..'..'......:...^:._. -.:....
:.::.'::..'_'.;,.'.:i:....':...::....'.':.:, À :::::: Àe a tee ee. e ce. ate ladle. To improve the hafnium dispersion, the molten alloy is preferably stirred before pouring...DTD: Any type of hafnium can be used, but electrolytic hafnium 5 is preferred. The hafnium particles are preferably reduced in size as much as possible, for example, by grinding to a fine powder in a suitable mill. The hafnium particles preferably have a particle size of less than 5 mm, preferably less than 4 mm, with an average of 10 from 1 to 2 mm. When dispersed in the melt, the hafnium particles are further reduced in size.
The alloys of the invention have a primary carbide network similar to the corresponding alloys without the 15 oxide dispersion. The primary carbides are mainly composed of chromium and/or iron carbo-nitrides, optionally with niobium, titanium and/or zirconium carbo-
nitrides also present. The invention also provides the possibility of obtaining a dispersion of secondary 20 carbides after the alloy has been brought to a high temperature. These secondary carbides are mainly chromium (or other elements such as iron) carbo-nitrides and optionally niobium, titanium (and/or zirconium) carbo-
nitrides. In additions to these precipitates, the invention provides for the formation of a hafoia / hafnium oxide dispersion (the hafnium can be oxidised to form HfO2, but it can be expected that there will also be formed an 30 oxide HfOX with x as a variable), and hafnium/niobium/titanium carbo-nitrides and (rarely) oxides mixtures (the quantity of niobium and titanium is variable as well as the nitrogen and the oxygen). It is also possible that some hafnium carbo-nitrides may be 35 formed. More numerous titanium nitride (or carbide)
:..1 ';.:.... '; 'lo.';.. ".':'t'::i'.;;t'.'.'.':...::...1 _ i:::.:.' ' '::. a! i:. a_:'.:.:':.1.':.'::'.;.i'. i::'..i:\'. &:: À À À À e À À
À TIC BC..e dispersions may be observed in the alloy, some of which may also contain hafnia particles.
The alloys of the invention have improved high 5 temperature creep resistance, leading to an improved service life expectancy. Without wishing to be confined to any particular theory, it is believed that the creep resistance of the new alloys derives from the ability of the particle dispersion to delay the motion of the 10 dislocations in the alloy lattice. The micro-alloy, without the oxide dispersion, can delay the motion of dislocations by the presence of carbide (and/or nitride) precipitates, but the presence of the oxide dispersion provides a substantial unexpected extra improvement.
The alloys of the invention can be formed into tubes, for example, by rotational moulding, and such rotationally moulded tubes are a further aspect of the invention. The rotational moulding process can provide a non-uniform 20 particle distribution in the tube wall, with the greater concentration of particles being towards the outer surface of the tube wall, and this can be beneficial in some cases. For example, in certain applications the internal bore of the tube is machined, removing 4-5 mm of 25 material; this gradient of concentration ensures that the hafnium/hafnia reinforcement is kept in the useful part of the tube. Other components that can be manufactured from the new alloys include fittings, fully fabricated ethylene furnace assemblies, reformer tubes and 30 manifolds.
A further advantage of the hafnium addition is that it can tend to improve the oxide layer adherence at the surface of an alloy tube. The alloy is able to develop an 35 oxide layer on its surface that protects it against
:.i '..i._i L.;;.;',!i.;;ti',i: i.i:..'i\ i it.. \'L I. _;.'.i' i. is.;:.. :i.'.. i:i & ÀÀ e Àeeece.e À c À À ac À Àe À Àe- a.- I. e.. e corrosion by carburisation. This protective oxide layer is formed ideally of chromium/manganese/silicon oxides, but can also include iron and nickel oxides. The oxide layer has a tendency to spell during the tube service 5 life (because of differences of coefficients of expansion with the alloy, compressive stresses in the oxide, eta).
Spalling leaves the alloy unprotected against corrosion from the gaseous and particulate reactants of the ethylene cracking process. It has surprisingly been 10 found that the hafnium addition can tend to delay the spelling of the protective oxide layer.
Embodiments of alloys according to the invention are illustrated in the accompanying Drawings, by way of 15 example only, in which: Figure 1 is a photomicrograph of a first alloy according to the invention with its composition, Figure 2 is a photomicrograph of a second alloy according 20 to the invention with its composition; Figure 3 is a photomicrograph of a third alloy according to the invention with its composition; and Figure 4 is a photomicrograph of a fourth alloy acording to the invention with its composition.
The invention is further illustrated by the following Examples, in which all percentages are by weight: Example 1
The following melt composition is produced in a clean furnace: Nickel 25% 35 Chromium 35%
At; I'.,:;: it's I;.\..it i.i.;.i '..;. i.;.\ A,._..;; i:;\.) i: HA 'i. '; À e.e.ee ee À e C e e Àeeeseee..e e.e Carbon 0.4% Niobium 0.8 - 0.9% Silicon 1.6 - 1.8% Manganese 1.1 - 1.3% 5 Iron balance.
The temperature of the melt is raised to a tap temperature of 1640 C to 1650 C and the silicon content checked. The furnace is then de-slaged, removing as much 10 slag as possible. lOOkg of alloy are then tapped into a ladle and 0.35% hafnium particles of particle size maximum 5 mm, average 1 -2 mm, are added to the tap stream. After the hafnium addition, 0.18% titanium, in the form of FeTi is added to the ladle.
The alloy in the ladle is stirred and immediately poured into a tube mould.
The creep resistance properties of the alloy thus 20 produced were compared with the properties of an otherwise identical commercial alloy from which the hafnium addition was omitted.
The results of a Larson-Miller plot of the stress-rupture 25 properties of the commercial alloy derived from the regression analysis of numerous creep tests gave a typical figure of 16.7 MPa at a temperature of 1100 C.
The commercial alloy is expected to fail after a minimum of 100 hours, with a mean value failure of 275 hours.
30 The alloy according to the invention had a minimum failure time of rupture of 370 hours and a mean value failure of 430 hours.
Example 2
'..'\,.';;.j'#.;'\:,'j.i.'..i''.. -'i''-.';..'.S..'.''. C\i;','i.',i.\'.'.'.'.i.:'.';:;'..;..;i.'.i.''''.'.'..'".'.'...i.'.;-.-..-' \..'..'.'.i;.
À e À e c À À À À À C
À À À e À À see ce. ee. Àe À see The procedure of Example 1 is repeated using the same melt composition except that the titanium addition is omitted. 5 The creep resistance properties of the alloy thus produced were compared with the properties of an otherwise identical commercial alloy from which the hafnium addition was omitted.
10 The results of a Larson-Miller plot of the stress-rupture properties of the commercial alloy derived from the regression analysis of numerous creep tests gave a typical figure of 16.2 MPa at a temperature of 1100 C.
The commercial alloy is expected to fail after a minimum 15 of 100 hours, with a mean value failure of 202 hours.
The alloy according to the invention had a minimum failure time of rupture of 396 hours, a mean value failure of 430 hours and a maximum failure time of rupture of 629 hours.
The results of Examples 1 and 2 show the dramatic improvement in creep properties that can be obtained using the alloys and method of the invention.
25 The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application
and which are open to public inspection with this specification, and the contents of all such papers and
30 documents are incorporated herein by reference.
All of the features disclosed in this specification
(including any accompanying claims, abstract and drawings), and/or all of the- steps of any method or 35 process so disclosed, may be combined in any combination,
;I'',\.;..'i:',t'iiiY''.\',' 'I. '.4'; ''. hi'.'.'.\:'.:4'..'47. \'l' 'a::;.;:; hi".'.'.;:..'..i'.';::i,;,.i'.':,';..
ee e e e.eccecc e e e #ece e e e e e c c cce c e seeeeeeceec e e ce.
except combinations where at least some of such features and/or steps are mutually exclusive.
Each feature disclosed in this specification (including
5 any accompanying claims, abstract and drawings), may be replaced by alternative features serving the same, equivalent or similar purpose, unless expressly stated otherwise. Thus, unless expressly stated otherwise, each feature disclosed is one example only of a generic series 10 of equivalent or similar features.
The invention is not restricted to the details of any foregoing embodiments. The invention extends to any novel one, or any novel combination, of the features 15 disclosed in this specification (including any
accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
Claims (1)
- :'.C.; a: '.'.:.'.'^b.'N'.:.'i'':::.::::::":':i:.' I:::' \:;.': ',: i.',i.:1'.'. ':.::.'. \.:,::.'.::.:.::.::.: -.:.ii.:: ' ',:..;' 'l.' '. ::::::.::.!: ' ': ÀÀÀÀ ÀÀeÀc.eÀe e aÀCc À À ÀÀÀC À ÀeÀ À À Àee À. À- ece e Àe CLAIMS1. An oxide dispersion strengthened nickel-chromium 5 iron alloy comprising, by weight: Carbon 0.01 to 0. 5% Silicon 0.01 to 2. 5% Manganese O to 2. 5% 10 Nickel 15 to 50% Chromium 20 to 40% Molybdenum O to 1. 0% Niobium O to 1. 7% Titanium O to 0.5% 15 zirconium. O to 0. 5% Cobalt O to 2. 0% Tungsten O to 1. 0% Hafnium 0.01 to 4. 5%, 20 balance iron and incidental impurities, with the proviso that at least one of niobium, titanium and zirconium is present and that at least part of the hafoium is present as finally divided oxide particles.2. An alloy according to claim 1 having the following composition, by weight: Carbon 0.3 to 0.5% 30 Silicon 0.1 to 2.5% Manganese 2.5% max.Nickel 30 to 40% Chromium 20 to 30% Molybdenum 1. 0% max.35 Niobium 1.7% max.i it;,,,, j.,I,,,;;t,,, jut\.,Y,, i,, A;, jeer i to L.; I,, I],, cup,,,, i,,,j ej -in ion -:::r.:: ÀÀ À Àe. À.ee ee Àeee À e Àe.eceeBe,,,.e Hafnium 0.01 to 4.5% Titanium 0.5% max.Zirconium 0.5% max.Cobalt 2.0% max.5 Tungsten 1.0% max., Balance iron and incidental impurities.3. An alloy according to claim 1 having the following composition, by weight: Carbon 0.03 to 0.2% Silicon 0.1 to 0.25% Manganese 2.5% max.Nickel 30 to 40% 15 Chromium 20 to 30% Molybdenum 1.0% max.Niobium 1.7% max.Hafnium 0.01 to 4.5% Titanium 0.5% max.20 Zirconium 0.5% max.Cobalt 2.05% max.Tungsten 1.0% max., balance iron and incidental impurities.4. An alloy according to claim 1 having the following composition, by weight: Carbon 0.3 to 0.5% 30 Silicon 0.1 to 2.5% Manganese 2.5% max.Nickel 40 to 50% Chromium 30 to 40% Molybdenum 1.0% max.35 Niobium 1.7% max.:.:;;:;.:.::.:.' _. a.:. i:;.':.;.':.;:::.'=.:':_i.:.'.;.'.:!':.'.;.-.:. ::;::!' ';:.i:'.::..'.. ti: ';;i' '..\.i.:i _..'.u..CC C ce.ehehe c À ÀÀe À -À ace can see ee. eve Hafnium 0.01 to 4.5% Titanium 0.5% max.Zirconium 0.5% max.Cobalt 2.0% max.5 Tungsten 1.0% max., balance iron and incidental impurities.5. An alloy according to claim 1 having the following 10 composition, by weight: Carbon 0.03 to 0.2% Silicon 0.1 to 2.5% Manganese 2.5% max.15 Nickel 40 to 50% Chromium 30 to 40% Molybdenum 1.0% max.Niobium 1.7% max.Hafnium 0.01 to 4.5% 20 Titanium 0.5% max.Zirconium 0.5% max.Cobalt 2.0% max.Tungsten 1.0% max., 25 balance iron and incidental impurities.6. An alloy according to claim 1 having the following composition, by weight: 30 Carbon 0.3 to 0.5% Silicon 0.1 to 2.5% Manganese 2.5% max.Nickel 19 to 22% Chromium 24 to 27% 35 Molybdenum 1.0% max.:4',:.'t.',.'bi't;." 'A;X';'.i';;.';i&i i'.; i..'\i.;;';ii;'-' 'it 'ii 'I t C 8se 84 88 À À 8 À À 8 888 e À À eÀ; À 8 me 868 I À. 8 '..Niobium 1.7% max Hafoium 0.01 to 4.5% Cobalt 2.0% max.Tungsten 1.0% max., balance iron and incidental impurities.7. An alloy according to claim 1 having the following composition, by weight: Carbon 0.03 to 0.2% Silicon 0.1 to 2.5% Manganese 2.5% max Nickel 30 to 45% 15 Chromium 19 to 22% Molybdenum 1.0% max.Niobium 1.7% max.Hafnium 0.01 to 4.5% Titanium 0.5% max.20 Zirconium 0.5% max.Cobalt 2.0% max.Tungsten 1.0% max., balance iron and incidental impurities.8. An alloy according to any of the preceding claims, in which the amount of hafnium in the alloy, by weight, is from 0.01 to 3.0%.30 9. An alloy according to any of the preceding claims, in which the amount of hafnium in the alloy, by weight, is from 0.1% to 1.0%.10. An alloy according to any of the preceding claims, 35 in which the amount of hafnium in the alloy, by weight,\;.; 'i'.iec;.;;i"ldi ' i ':: It'd:.'::. 3::'.'; ':.',':.'.;.'.i.'.':.i.'. ':;.:.'.b k' 'i.&'. ':'.';.'i '' 'y' -i,: '.':.i\.:tu.:.:i;.,:.;. i. i; ::: eee e e e'Heeee8 e e e e I e e e e e e e e e e e e I e e I 8 e Use ese see ele ese.is from 0.2 to 0.5%.11. An alloy according to any of the preceding claims, in which the hafnium is present in the alloy in the form 5 of finally divided oxidised particles having an average particle size of from 50 microns to 0.25 microns, or less. 12. An alloy according to any of the preceding claims, 10 in which the hafnium is present in the alloy in the form of finally divided oxidised particles having an average particle size of from 5 microns to 0.25 microns, or less.13. An alloy having the following composition, by 15 weight: Carbon 0.45% Silicon 1.3% Manganese 0.9% 20 Nickel 33.8% Chromium 25.7% Molybdenum 0. 03% Niobium 0.85% Hafnium 0.25% 25 Titanium 0.1% Zirconium 0.01% Cobalt 0. 4% Tungsten 0.01%, 30 balance iron and incidental impurities.14. An alloy according to any of the preceding claims substantially as described in the Examples.35 15. A nickel-chromium iron alloy comprising up to about,; ID,,; a_. bin','_:i'ii '.' ',?,,,ji,,t,':,::,,:';,.-,::,'t i.:;:,';: i, :,'.,,, ?.-.,; '.:':..;i MA.;. ?. ?;._; ÀeÀe À e Àee.eeee À e e e eeee e e e Àeee e e e eeee e e e seeaceeeesee e see 5% of hafnium-containing particles.16. A method of manufacturing an oxide dispersion strengthened nickelchromium-iron alloy which comprises 5 adding finely divided hafnium particles to a melt of the alloy before pouring, under conditions such that at least part of the hafnium is converted to oxide in the melt.17. A method according to claim 16, in which the alloy 10 is an alloy as claimed in any of claims 1 to 15.18. A method according to claim 16 or 17, wherein the hafnium particles have a particle size of less than 5mm.15 19. A method according to any of claims 16 to 18, in which the amount of hafnium added to the melt is from 0.01 to 3.0% by weight.20. A method according to any of claims 16 to 19, 20 wherein the hafnium particles are added to the melt shortly before pouring the molten alloy into the mould.21. A method according to claim 20, in which the hafnium particles are added to the molten alloy in a ladle.22. A method according to any of claims 16 to 21, in which the hafnium is electrolytic hafnium.23. A method according to any of claims 16 to 22, in 30 which the alloy melt is substantially aluminium free.24. A method according to any of claims 16 to 23, wherein the level of oxygen in the melt is varied by additions of one or more of niobium, titanium and 35 zirconium.:i.::.:: At:::.:: ÀÀeÀ cee.ÀeÀe À e ÀÀÀÀ À e ÀÀÀÀ ÀÀÀÀÀ ÀÀe ee. À. Àe À À..25. A method according to claim 24, in which the titanium is added in the form of TiFe after the hafnium addition. 26. A method according to any of claims 16 to 24, in which the maximum amount of slag is removed from the surface of the alloy.10 27. A method according to any of claims 16 to 26, in which the melt temperature is in the range of from 1580 C to 1700 C.28. A method according to any of claims 16 to 27, in 15 which the alloy is formed into a tube by rotational moulding. 29. A method according to any of claims 16 to 28 substantially as described in the Examples.30. A method of manufacturing a nickel-chromium-iron alloy, which comprises adding finely divided hafnium particles to the melt before pouring.25 31. A creep resistant alloy tube formed from a nickel-chromium-iron alloy comprising up to about 5% of hafnium-containing particles.32. A tube according to claim 31, which comprises an 30 oxide dispersion strengthened nickel-chromium-iron alloy comprising up to about 5% of hafnium 33. A nickel-chromium-iron alloy tube comprising up to about 5% of hafnium-containing particles substantially as 35 hereinbefore described.V'I'',;_'\itI. '.:.; i Ike YLg:;;t:;;: id;;; it; \;eq;\{:,n,; j,_l,j, ÀeeÀ Àee.ÀeÀe À Àeee e À Àeee e e Àeee e À ce.Àe.seeÀee À eee 34. A tube formed from an alloy according to any of claims 1 to 15 by rotational moulding.5 35. A nickel-chromium-iron alloy having a structure and composition substantially as described and illustrated in Figures 1 to 4 of the accompanying Drawings, wherein the tables represent percentages by weight of the alloy constituents.
Priority Applications (20)
Application Number | Priority Date | Filing Date | Title |
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GB0225648A GB2394959A (en) | 2002-11-04 | 2002-11-04 | Hafnium particle dispersion hardened nickel-chromium-iron alloys |
GBGB0228576.5A GB0228576D0 (en) | 2002-11-04 | 2002-12-09 | High temperature alloys |
GB0324859A GB0324859D0 (en) | 2002-11-04 | 2003-10-24 | High temperature alloys |
US10/533,034 US20070144622A1 (en) | 2002-11-04 | 2003-10-30 | High temperature resistant alloys |
AT03775499T ATE404706T1 (en) | 2002-11-04 | 2003-10-30 | HIGH TEMPERATURE RESISTANT ALLOYS |
GB0325297A GB2394960B (en) | 2002-11-04 | 2003-10-30 | High temperature alloys |
EP03775499A EP1558776B8 (en) | 2002-11-04 | 2003-10-30 | High temperature resistant alloys |
EP08153580A EP1935996A1 (en) | 2002-11-04 | 2003-10-30 | High temperature resistant alloys |
ES03775499T ES2312831T3 (en) | 2002-11-04 | 2003-10-30 | HIGH TEMPERATURE RESISTANT ALLOYS. |
AU2003283525A AU2003283525A1 (en) | 2002-11-04 | 2003-10-30 | High temperature resistant alloys |
PCT/GB2003/004665 WO2004042100A2 (en) | 2002-11-04 | 2003-10-30 | High temperature resistant alloys |
JP2004549307A JP2006505694A (en) | 2002-11-04 | 2003-10-30 | High temperature alloy |
DE60322935T DE60322935D1 (en) | 2002-11-04 | 2003-10-30 | HIGH TEMPERATURE RESISTANT ALLOYS |
EP03810516A EP1560940A2 (en) | 2002-11-04 | 2003-11-04 | High temperature alloys |
PCT/GB2003/004754 WO2004042101A2 (en) | 2002-11-04 | 2003-11-04 | High temperature alloys |
CA002504937A CA2504937A1 (en) | 2002-11-04 | 2003-11-04 | Tube made from high temperature alloys |
AU2003301837A AU2003301837A1 (en) | 2002-11-04 | 2003-11-04 | High temperature alloys |
JP2004549337A JP2006517255A (en) | 2002-11-04 | 2003-11-04 | High temperature alloy |
US10/533,850 US20060096673A1 (en) | 2002-11-04 | 2004-11-04 | High temperature alloys |
US12/561,057 US20100175508A1 (en) | 2002-11-04 | 2009-09-16 | High temperature alloys |
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GB0225648A GB2394959A (en) | 2002-11-04 | 2002-11-04 | Hafnium particle dispersion hardened nickel-chromium-iron alloys |
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GB2394959A true GB2394959A (en) | 2004-05-12 |
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GBGB0228576.5A Ceased GB0228576D0 (en) | 2002-11-04 | 2002-12-09 | High temperature alloys |
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EP (1) | EP1560940A2 (en) |
JP (1) | JP2006517255A (en) |
AT (1) | ATE404706T1 (en) |
AU (1) | AU2003301837A1 (en) |
CA (1) | CA2504937A1 (en) |
DE (1) | DE60322935D1 (en) |
ES (1) | ES2312831T3 (en) |
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US8318083B2 (en) * | 2005-12-07 | 2012-11-27 | Ut-Battelle, Llc | Cast heat-resistant austenitic steel with improved temperature creep properties and balanced alloying element additions and methodology for development of the same |
CN109112327A (en) * | 2018-11-08 | 2019-01-01 | 北京钢研高纳科技股份有限公司 | A kind of anti-oxidant heat-resisting alloy and preparation method |
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GB2394959A (en) * | 2002-11-04 | 2004-05-12 | Doncasters Ltd | Hafnium particle dispersion hardened nickel-chromium-iron alloys |
JP2006505694A (en) * | 2002-11-04 | 2006-02-16 | ドンカスターズ リミテッド | High temperature alloy |
US7824606B2 (en) * | 2006-09-21 | 2010-11-02 | Honeywell International Inc. | Nickel-based alloys and articles made therefrom |
FR2939808B1 (en) * | 2008-12-16 | 2011-01-07 | Air Liquide | HIGH-TEMPERATURE STABLE-NICKEL-CHROME ALLOY ALLOYS |
CN103087739A (en) * | 2013-02-04 | 2013-05-08 | 安徽省建辉可再生能源科技有限公司 | Biomass material thermal cracking furnace and material thereof, and method for preparing natural gas by using biomass material thermal cracking furnace |
CN105463288B (en) * | 2016-01-27 | 2017-10-17 | 大连理工大学 | Casting alloy of high-strength high-plastic anti-chlorine ion corrosion and preparation method thereof |
FR3082209B1 (en) * | 2018-06-07 | 2020-08-07 | Manoir Pitres | AUSTENITIC ALLOY WITH HIGH ALUMINUM CONTENT AND ASSOCIATED DESIGN PROCESS |
JP7131318B2 (en) * | 2018-11-14 | 2022-09-06 | 日本製鉄株式会社 | austenitic stainless steel |
CN113005333B (en) * | 2021-02-23 | 2022-04-01 | 江苏兄弟合金有限公司 | Ultra-high temperature nickel-based alloy and preparation method thereof |
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2003
- 2003-10-30 AT AT03775499T patent/ATE404706T1/en not_active IP Right Cessation
- 2003-10-30 DE DE60322935T patent/DE60322935D1/en not_active Expired - Lifetime
- 2003-10-30 ES ES03775499T patent/ES2312831T3/en not_active Expired - Lifetime
- 2003-11-04 CA CA002504937A patent/CA2504937A1/en not_active Abandoned
- 2003-11-04 WO PCT/GB2003/004754 patent/WO2004042101A2/en not_active Application Discontinuation
- 2003-11-04 AU AU2003301837A patent/AU2003301837A1/en not_active Abandoned
- 2003-11-04 JP JP2004549337A patent/JP2006517255A/en not_active Withdrawn
- 2003-11-04 EP EP03810516A patent/EP1560940A2/en not_active Withdrawn
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JPS63259051A (en) * | 1987-04-14 | 1988-10-26 | Nippon Steel Corp | High toughness steel for electric resistance welded steel tube having excellent sour resistance |
EP0384608A1 (en) * | 1989-02-08 | 1990-08-29 | Inco Alloys International, Inc. | Mechanically alloyed nickel-cobalt-chromium-iron composition of matter |
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US8318083B2 (en) * | 2005-12-07 | 2012-11-27 | Ut-Battelle, Llc | Cast heat-resistant austenitic steel with improved temperature creep properties and balanced alloying element additions and methodology for development of the same |
CN109112327A (en) * | 2018-11-08 | 2019-01-01 | 北京钢研高纳科技股份有限公司 | A kind of anti-oxidant heat-resisting alloy and preparation method |
CN109112327B (en) * | 2018-11-08 | 2019-09-03 | 青岛新力通工业有限责任公司 | A kind of anti-oxidant heat-resisting alloy and preparation method |
Also Published As
Publication number | Publication date |
---|---|
GB0225648D0 (en) | 2002-12-11 |
ES2312831T3 (en) | 2009-03-01 |
ATE404706T1 (en) | 2008-08-15 |
WO2004042101A2 (en) | 2004-05-21 |
WO2004042101B1 (en) | 2004-09-30 |
EP1560940A2 (en) | 2005-08-10 |
JP2006517255A (en) | 2006-07-20 |
US20100175508A1 (en) | 2010-07-15 |
CA2504937A1 (en) | 2004-05-21 |
WO2004042101A3 (en) | 2004-08-12 |
GB0228576D0 (en) | 2003-01-15 |
AU2003301837A1 (en) | 2004-06-07 |
US20060096673A1 (en) | 2006-05-11 |
DE60322935D1 (en) | 2008-09-25 |
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