EP2746414B1 - Alliages ni-cr-mo-cu résistants aux acides et alcalins dotés de contenus critiques de chrome et de cuivre - Google Patents
Alliages ni-cr-mo-cu résistants aux acides et alcalins dotés de contenus critiques de chrome et de cuivre Download PDFInfo
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- EP2746414B1 EP2746414B1 EP13005102.2A EP13005102A EP2746414B1 EP 2746414 B1 EP2746414 B1 EP 2746414B1 EP 13005102 A EP13005102 A EP 13005102A EP 2746414 B1 EP2746414 B1 EP 2746414B1
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- chromium
- alloys
- nickel
- molybdenum
- alloy
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- 239000010949 copper Substances 0.000 title claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 21
- 239000011651 chromium Substances 0.000 title claims description 21
- 229910052802 copper Inorganic materials 0.000 title claims description 21
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 20
- 229910052804 chromium Inorganic materials 0.000 title claims description 20
- 229910000881 Cu alloy Inorganic materials 0.000 title claims description 17
- 239000002253 acid Substances 0.000 title description 9
- 239000003513 alkali Substances 0.000 title 1
- 229910045601 alloy Inorganic materials 0.000 claims description 98
- 239000000956 alloy Substances 0.000 claims description 98
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 84
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 47
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 46
- 238000005260 corrosion Methods 0.000 claims description 38
- 230000007797 corrosion Effects 0.000 claims description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052799 carbon Inorganic materials 0.000 claims description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 27
- 239000012535 impurity Substances 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 239000010936 titanium Substances 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- 229910052719 titanium Inorganic materials 0.000 claims description 16
- FJPKZVUTEXZNPN-UHFFFAOYSA-N chromium copper molybdenum nickel Chemical compound [Ni][Cu][Cr][Mo] FJPKZVUTEXZNPN-UHFFFAOYSA-N 0.000 claims description 14
- 239000010955 niobium Substances 0.000 claims description 14
- 229910052742 iron Inorganic materials 0.000 claims description 13
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052735 hafnium Inorganic materials 0.000 claims description 11
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 239000011777 magnesium Substances 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000005242 forging Methods 0.000 claims description 2
- 238000004663 powder metallurgy Methods 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 26
- 238000012360 testing method Methods 0.000 description 12
- 229910000990 Ni alloy Inorganic materials 0.000 description 11
- 150000007513 acids Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 229910001182 Mo alloy Inorganic materials 0.000 description 6
- OGSYQYXYGXIQFH-UHFFFAOYSA-N chromium molybdenum nickel Chemical compound [Cr].[Ni].[Mo] OGSYQYXYGXIQFH-UHFFFAOYSA-N 0.000 description 6
- 150000001247 metal acetylides Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000788 chromium alloy Substances 0.000 description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000035515 penetration Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007792 addition Methods 0.000 description 3
- 238000005275 alloying Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010410 dusting Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- XRBURMNBUVEAKD-UHFFFAOYSA-N chromium copper nickel Chemical compound [Cr].[Ni].[Cu] XRBURMNBUVEAKD-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000010309 melting process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 229910018054 Ni-Cu Inorganic materials 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910018481 Ni—Cu Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- VVTSZOCINPYFDP-UHFFFAOYSA-N [O].[Ar] Chemical compound [O].[Ar] VVTSZOCINPYFDP-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 238000010349 cathodic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- VNTLIPZTSJSULJ-UHFFFAOYSA-N chromium molybdenum Chemical compound [Cr].[Mo] VNTLIPZTSJSULJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910021652 non-ferrous alloy Inorganic materials 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/0433—Nickel- or cobalt-based alloys
-
- 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
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/053—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 30% but less than 40%
-
- 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
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
- C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
Definitions
- This invention relates generally to non-ferrous alloy compositions, and more specifically to nickel-chromium-molybdenum-copper alloys that provide a useful combination of resistance to 70% sulfuric acid at 93°C and resistance to 50% sodium hydroxide at 121°C.
- Certain nickel alloys are very resistant to strong, hot sulfuric acid. Others are very resistant to hot, strong sodium hydroxide. However, none possesses adequate resistance to both chemicals.
- nickel alloys with high alloy contents are used to resist sulfuric acid and other strong acids, the most resistant being the nickel-molybdenum and nickel-chromium-molybdenum alloys.
- pure nickel (UNS N02200/Alloy 200) or nickel alloys with low alloy contents are the most resistant to sodium hydroxide. Where higher strength is required, the nickel-copper and nickel-chromium alloys are used. In particular, alloys 400 (Ni-Cu, UNS N04400) and 600 (Ni-Cr, UNS N06600) possess good resistance to corrosion in sodium hydroxide.
- 70 wt.% sulfuric acid is well known to be very corrosive to metallic materials, and is the concentration at which the resistance of many materials (including the nickel-copper alloys) breaks down, as a result of changes in the cathodic reaction (from reducing to oxidizing).
- 50 wt.% sodium hydroxide is the concentration most widely used in industry. A higher temperature was used in the case of sodium hydroxide to increase internal attack (the main form of degradation of nickel alloys in this chemical), hence increase the accuracy of measurements during subsequent cross-sectioning and metallographic examination.
- U.S. Patent No. 6,280,540 to Crook discloses copper-containing, nickel-chromium-molybdenum alloys which have been commercialized as C-2000® alloy and correspond to UNS 06200. These contain higher molybdenum levels and lower chromium levels than in the alloys of this invention and lack the aforementioned corrosion characteristics.
- U.S. Patent No. 6,623,869 to Nishiyama et al. describes nickel-chromium-copper alloys for metal dusting service at high temperatures, the maximum copper contents of which are 3 wt.%. This is below the range required for resistance to 70% sulfuric acid at 93°C and 50% sodium hydroxide at 121°C. More recent U.S. Patent Application Publications ( US 2008/0279716 and US 2010/0034690) by Nishiyama et al. describe additional alloys for resistance to metal dusting and carburization. The alloys of US 2008/0279716 differ from the alloys of this invention in that they have a molybdenum restriction of not more than 3%.
- the alloys of US 2010/0034690 are in a different class, being iron-based, rather than nickel-based, with a molybdenum content of 2.5% or less.
- U.S. Published Patent Application No. US2011/0236252 to Ueyama et al. discloses nickel-chromium-molybdenum-copper alloys resistant to reducing hydrochloric and sulfuric acids. The given range in these alloys for chromium is 20 to 30% and for copper it is 2 to 5%; however, the inventive alloy examples given in this patent contain chromium up to 23% and copper up to 3.06%, which are below the levels needed for resistance to 70% sulfuric at 93°C and 50% sodium hydroxide at 121°C.
- the principal object of this invention is to provide alloys, capable of being processed into wrought products (sheets, plates, bars, etc.), which exhibit a useful and elusive combination of resistance to 70% sulfuric acid at 93°C (200°F) and resistance to 50% sodium hydroxide at 121°C (250°F).
- These highly desirable properties have been unexpectedly attained using a nickel base, chromium between 30 and 33 wt.%, molybdenum between 5.0 and 6.2 wt.%, and copper between 3.5 and 4.0 wt.%.
- chromium contents between 30 and 33 wt.% the full range of copper (3.5 to 4.0 wt.%) provides these highly desirable properties.
- such alloys typically contain small quantities of aluminum and manganese (up to about 0.4 and 0.7 wt.%, respectively in the nickel-chromium-molybdenum alloys), and possibly traces of magnesium and the rare earth elements (up to about 0.05 wt.%).
- Iron is the most likely impurity in such alloys, due to contamination from other nickel alloys melted in the same furnaces, and maxima of 2.0 or 3.0 wt.% are typical of those nickel-chromium-molybdenum alloys that do not require an iron addition. In our experiments, iron contents up to 1.5 wt.% were found to be acceptable.
- alloys of this invention should be able to tolerate these impurities at the levels commonly encountered in the nickel-chromium-molybdenum alloys. Also, alloys of such high chromium content cannot be air melted without some pick up of nitrogen. It is usual, therefore, in high chromium nickel alloys to allow up to 0.13 wt.% maximum of this element.
- the successful alloys in our experiments contained between 0.02 and 0.10 wt.%.
- Alloy G with a carbon content of 0.002 wt.% could not be processed into wrought products.
- a carbon range of 0.02 to 0.10 wt.% is preferred.
- silicon a range of 0.1 to 0.6 wt.% is preferred, based on the fact that levels at each end of this range provided satisfactory properties.
- microstructural stabilities of these alloys at elevated temperatures can be improved by encouraging the formation of MC carbides, which are very stable.
- compositional range defined above involved study of a wide range of nickel-based compositions, of varying chromium, molybdenum, and copper contents. These compositions are presented in Table 1. For comparison, the compositions of the commercial alloys used to resist either 70% sulfuric acid or 50% sodium hydroxide are included in Table 1. Table 1: Compositions of Experimental and Commercial Alloys Alloy Ni Cr Mo Cu Fe Mn Al Si C Other A Bal. 27 7.8 6.0 1.1 0.3 0.2 0.1 0.03 B Bal. 27 7.5 5.9 1.1 0.3 0.3 0.1 0.01 C Bal. 28 7.3 3.1 1.1 0.3 0.3 0.1 0.01 D Bal. 30 8.2 2.6 0.9 0.3 0.5 0.1 0.03 E Bal.
- the experimental alloys were made by vacuum induction melting (VIM), then electro-slag re-melting (ESR), at a heat size of 13.6 kg. Traces of nickel-magnesium and/or rare earths were added to the VIM furnace charges, to help minimize the sulfur and oxygen contents of the experimental alloys.
- the ESR ingots were homogenized, hot forged, and hot rolled into sheets of thickness 3.2 mm for test. Surprisingly, three of the alloys (G, K, and L) cracked so badly during forging that they could not be hot rolled into sheets for testing. Those alloys which were successfully rolled to the required test thickness were subjected to annealing trials, to determine (by metallographic means) the most suitable annealing treatments.
- Corrosion tests were performed on samples measuring 25.4 x 25.4 x 3.2 mm. Prior to corrosion testing, surfaces of all samples were manually ground using 120 grit papers, to negate any surface layers and defects that might affect corrosion resistance.
- the tests in sulfuric acid were carried out in glass flask/condenser systems.
- the tests in sodium hydroxide were carried out in TEFLON systems, since glass is attacked by sodium hydroxide. A time of 96 hours was used for the sulfuric acid tests, with interruptions every 24 hours to enable samples to be weighed, while a duration of 720 hours was used for the sodium hydroxide tests. Two samples of each alloy were tested in each environment, and the results averaged.
- the primary mode of degradation In sulfuric acid, the primary mode of degradation is uniform attack, thus average corrosion rates were calculated from weight loss measurements.
- the primary mode of degradation In sodium hydroxide, the primary mode of degradation is internal attack, which is either a uniform attack or more aggressive form of internal "dealloying" attack. Dealloying generally refers to the leaching of certain elements (for example, molybdenum) from the alloy, which often degrades the mechanical properties as well.
- the maximum internal attack can only be measured by sectioning the samples and studying them metallographically. The values presented in Table 2 represent measured maximum internal penetration in the alloy cross-section.
- a pass/fail criterion of 0.45 mm/y (of uniform attack, in the case of sulfuric acid, and of maximum internal penetration, in the case of sodium hydroxide) was used. Alloys exhibiting corrosion rates of 0.45 mm/y or more are considered to be unacceptable.
- the basis for this criterion is related to iso-corrosion diagrams, which are used by industries to determine if alloys are acceptable or unacceptable at specified concentrations and temperatures in different chemicals. Several samples or test coupons of the alloy being considered are tested and the corrosion rate for each test is plotted. Then a line is fitted to the data points.
- corrosion rates between 0.45 and 0.55 mm/y will often result in a plot line of 0.5 mm/y to take into account random and systematic variations. For many applications the art considers a corrosion rate of less than 0.5 mm/y to be acceptable. However, because alloys which have corrosion rates between 0.45 and 0.55 mm/y could be considered to have a corrosion rate of 0.5 mm/y, we concluded that corrosion rates must be below 0.45 mm/y to be acceptable and set that performance requirement for alloys of this invention.
- Table 2 reveals that alloys of the present invention corrode at low enough rates in 70% sulfuric acid to be useful industrially at 93°C and exhibit internal penetration rates that correspond to significantly less than 0.5 mm/y in 50% sodium hydroxide at 121°C. Interestingly, unlike the nickel-chromium-molybdenum alloys with high molybdenum contents (C-4, C-22, C-276, and C-2000), none of the alloys of this invention exhibited a dealloying form of corrosion attack.
- the required copper range of 3.5 to 4.0 wt.% and the proviso that if chromium is below 30 wt.%, then copper must be at least 4.7 wt.% are based on the results for several alloys, in particular A, B, C, E, and N.
- the relationships between chromium and copper are likely due to their respective influences on protective films in 70% sulfuric acid. It is known, for example, that chromium induces chromium rich passive films on metallic surfaces in oxidizing acids, and that copper can provide protection in concentrated sulfuric acid by plating metallic surfaces. Alloys K and L, with higher copper contents could not be forged.
- the chromium range is based on the results for Alloys A and O (with contents of 27 and 33 wt.%, respectively).
- the molybdenum range is based on the results for Alloys H and A (with contents of 4.9 and 7.8 wt.%, respectively), and the suggestion of U.S. Patent No. 6,764,646 , which indicates that molybdenum contents below 4.9 wt.% do not provide sufficient resistance to general corrosion of the nickel-chromium-molybdenum-copper alloys. This is important for neutralizing systems containing other chemicals.
- Chromium (Cr) is a primary alloying element, known to improve the performance of nickel alloys in oxidizing acids. When combined with molybdenum and copper (where special relationships apply), it has been shown to provide the desired corrosion resistance to both 70% sulfuric acid and 50% sodium hydroxide in the range 30 to 33 wt.%.
- Molybdenum (Mo) is also a primary alloying element, known to enhance the corrosion-resistance of nickel alloys in reducing acids. In the range 5.0 to 6.2 wt.%, it contributes to the exceptional performance of the alloys of this invention in 70% sulfuric acid and 50% sodium hydroxide.
- Copper (Cu) between 3.5 wt.%, and 4.0 wt.%, and in combination with the abovementioned levels of chromium and molybdenum, produces alloys with unusual and unexpected resistance to acids and alkalis, in the form of 70% sulfuric acid at 93°C and 50% sodium hydroxide at 121°C.
- Iron (Fe) is a common impurity in nickel alloys. Iron contents of up to 1.5 wt.% have been found to be acceptable in the alloys of this invention.
- Manganese (Mn) is used to minimize sulfur in such alloys, and contents between 0.3 and 0.7 wt.% were found to result in successful alloys (from processing and performance standpoints).
- Aluminum (Al) is used to minimize oxygen in such alloys, and contents between 0.1 and 0.4 wt.% were found to result in successful alloys.
- Silicon (Si) is not normally required in corrosion-resistant nickel alloys, but is introduced during argon-oxygen decarburization (for those alloys melted in air). A small quantity of silicon (in the range 0.1 to 0.6 wt.%) was found to be essential in the alloys of this invention, to ensure forgeability.
- carbon (C) is not normally required in corrosion-resistant nickel alloys, but is introduced during carbon arc melting (for those alloys melted in air).
- a small quantity of carbon in the range 0.02 to 0.10 wt.%) was found to be essential in the alloys of this invention, to ensure forgeability.
- Mg magnesium
- rare earth elements are often included in such alloys for control of unwanted elements, for example sulfur and oxygen.
- the usual range of up to 0.05 wt.% is preferred for each of these elements in the alloys of this invention.
- Nitrogen (N) is easily absorbed by high chromium nickel alloys in the molten state, and it is usual to allow a maximum of 0.13 wt.% of this element in alloys of this kind.
- impurities that might occur in such alloys, due to contamination from previously-used furnace linings or within the raw charge materials, include cobalt, tungsten, sulfur, phosphorus, oxygen, and calcium.
- MC carbides are much more stable than the M 7 C 3 , M 6 C, and M 23 C 6 carbides normally encountered in chromium- and molybdenum-containing nickel alloys. Indeed, it should be possible to control the levels of these MC-forming elements so as to tie up as much carbon as is deemed suitable to control the level of carbide precipitation in the grain boundaries. In fact, the MC-former level could be fine-tuned during the melting process, depending upon the real-time measurement of carbon content.
- the MC-former level could be matched to the carbon level to avoid appreciable grain boundary carbide precipitation (a so-called “stabilized” structure).
- nitrogen is likely to compete with carbon, resulting in nitrides or carbonitrides of the same active former (e.g. titanium), which should therefore be present at a higher level (this can be calculated based on the real-time measurement of the nitrogen content).
- active former e.g. titanium
- Second is the unintended formation of gamma-prime (with titanium) or gamma-double prime (with niobium) phases; however, it should be possible to adjust the cooling and subsequent processing sequences to ensure that these elements are tied up in the form of carbides, nitrides, or carbonitrides.
- stabilized versions of these alloys for aqueous corrosion service might contain 0.05 wt.% carbon and 0.20 wt.% titanium.
- Those for elevated temperature service might contain 0.05 wt.% carbon and 0.15 wt.% titanium, to allow a controlled level of secondary, grain boundary precipitation to enhance creep resistance.
- niobium, hafnium, and tantalum are 92.9, 178.5, and 181.0, respectively.
- the niobium contents required to reap the same benefits are approximately double those for titanium.
- the hafnium or tantalum contents required to reap the same benefits are approximately quadruple those for titanium.
- niobium stabilized versions of these alloys for aqueous corrosion service might contain 0.05 wt.% carbon and 0.40 wt.% niobium (if the alloy does not contain any nitrogen), and 0.64 wt.% niobium, if the nitrogen impurity level is 0.035 wt.%.
- a carbon level of 0.11 wt.%, and a nitrogen impurity level of 0.035 wt.% 1.12 wt.% niobium might be required for aqueous corrosion service.
- Alloys for elevated temperature service in the absence of nitrogen impurities, might contain 0.05 wt.% carbon and 0.30 wt.% niobium.
- hafnium stabilized versions of these alloys for aqueous corrosion service might contain 0.05 wt.% carbon and 0.80 wt.% hafnium (if the alloy does not contain any nitrogen), and 1.28 wt.% hafnium, if the nitrogen impurity level is 0.035 wt.%.
- a carbon level of 0.11 wt.%, and a nitrogen impurity level of 0.035 wt.% 2.24 wt.% hafnium might be required for aqueous corrosion service.
- Alloys for elevated temperature service in the absence of nitrogen impurities, might contain 0.05 wt.% carbon and 0.60 wt.% hafnium.
- tantalum stabilized versions of these alloys for aqueous corrosion service might contain 0.05 wt.% carbon and 0.80 wt.% tantalum (if the alloy does not contain any nitrogen), and 1.28 wt.% tantalum, if the nitrogen impurity level is 0.035 wt.%.
- a carbon level of 0.11 wt.%, and a nitrogen impurity level of 0.035 wt.% 2.24 wt.% tantalum might be required for aqueous corrosion service.
- Alloys for elevated temperature service in the absence of nitrogen impurities, might contain 0.05 wt.% carbon and 0.60 wt.% tantalum.
- the alloys should exhibit comparable properties in other wrought forms, such as plates, bars, tubes, and wires, and in cast and powder metallurgy forms.
- the alloys of this invention are not limited to applications involving the neutralization of acids and alkalis. Indeed, they might have much broader applications in the chemical process industries and, given their high chromium and the presence of copper, should be useful in resisting metal dusting.
- the ideal alloy would comprise 31 wt.% chromium, 5.6 wt.% molybdenum, 3.8 wt.% copper, 1.0 wt.% iron, 0.5 wt.% manganese, 0.3 wt.% aluminum, 0.4 wt.% silicon, and 0.03 to 0.07 wt.% carbon, with a balance of nickel, nitrogen, impurities, and traces of magnesium and the rare earth elements (if used for the control of sulfur and oxygen).
- two alloys, Q and R, with this preferred nominal composition have been successfully melted, hot forged and rolled into sheet.
- a corresponding range would be 30 to 33 wt.% chromium, 5.0 to 6.2 wt.% molybdenum, 3.5 to 4.0 wt.% copper, up to 1.5 wt.% iron, 0.3 to 0.7 wt.% manganese, 0.1 to 0.4 wt.% aluminum, 0.1 to 0.6 wt.% silicon, and 0.02 to 0.10 wt.% carbon, with a balance of nickel, nitrogen, impurities, and traces of magnesium and the rare earths (if used for the control of sulfur and oxygen).
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Claims (10)
- Alliage de nickel-chrome-molybdène-cuivre résistant à l'acide sulfurique, ayant une vitesse de corrosion inférieure à 0,45 mm/an dans de l'acide sulfurique à 70 % à 93 °C pendant 96 heures et résistant à l'hydroxyde de sodium, ayant une attaque interne maximale correspondant à une vitesse de corrosion inférieure à 0,45 mm/an dans de l'hydroxyde de sodium à 50 % à 121 °C pendant 720 heures, consistant en :30 à 33 % en poids de chrome5,0 à 6,2 % en poids de molybdène3,5 à 4,0 % en poids de cuivrejusqu'à 1,5 % en poids de fer0,3 à 0,7 % en poids de manganèse0,1 à 0,4 % en poids d'aluminium0,1 à 0,6 % en poids de silicium0,02 à 0,10 % en poids de carbonejusqu'à 0,13 % en poids d'azotejusqu'à 0,05 % en poids de magnésiumjusqu'à 0,05 % en poids d'éléments des terres raresjusqu'à 0,015 % en poids de soufrejusqu'à 0,03 % en poids de phosphorejusqu'à 0,05 % en poids d'oxygènejusqu'à 0,05 % en poids de calcium ; eten tant qu'éléments facultatifs :jusqu'à 0,56 % en poids de titanejusqu'à 1,12 % en poids de niobiumjusqu'à 2,24 % en poids de tantale,jusqu'à 2,24 % en poids de hafniumjusqu'à 5,0 % en poids de cobaltjusqu'à 0,65 % en poids de tungstènele reste étant du nickel et des impuretés.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel les alliages sont sous des formes corroyées sélectionnées dans le groupe consistant en les tôles, les plaques, les barres, les fils, les tubes, les tuyaux et les pièces forgées.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage est sous forme coulée.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage est sous une forme de métallurgie des poudres.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, consistant en31 % en poids de chrome5,6 % en poids de molybdène3,8 % en poids de cuivre1,0 % en poids de fer0,5 % en poids de manganèse0,4 % en poids de silicium0,3 % en poids d'aluminium0,03 à 0,07 % en poids de carbonele reste étant du nickel et des impuretés.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage contient au moins un agent de formation de carbure MC sélectionné dans le groupe consistant en le titane, le niobium, le tantale et le hafnium.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage contient de 0,20 à 0,56 % en poids de titane.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage contient de 0,30 à 1,12 % en poids de niobium.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage contient de 0,60 à 2,24 % en poids de tantale.
- Alliage de nickel-chrome-molybdène-cuivre selon la revendication 1, dans lequel l'alliage contient de 0,60 à 2,24 % en poids de hafnium.
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Application Number | Priority Date | Filing Date | Title |
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US13/719,369 US9394591B2 (en) | 2012-04-30 | 2012-12-19 | Acid and alkali resistant nickel-chromium-molybdenum-copper alloys |
US13/871,405 US20130287624A1 (en) | 2012-04-30 | 2013-04-26 | STABILIZED ACID AND ALKALI RESISTANT Ni-Cr-Mo-Co ALLOYS |
US14/055,126 US9399807B2 (en) | 2012-04-30 | 2013-10-16 | Acid and alkali resistant Ni—Cr—Mo—Cu alloys with critical contents of chromium and copper |
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EP2746414A1 EP2746414A1 (fr) | 2014-06-25 |
EP2746414B1 true EP2746414B1 (fr) | 2019-12-11 |
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US3844774A (en) * | 1973-09-24 | 1974-10-29 | Carondelet Foundry Co | Corrosion-resistant alloys |
US4836985A (en) * | 1988-08-19 | 1989-06-06 | Carondelet Foundry Company | Ni-Cr-Fe corrosion resistant alloy |
US6280540B1 (en) | 1994-07-22 | 2001-08-28 | Haynes International, Inc. | Copper-containing Ni-Cr-Mo alloys |
JP3952861B2 (ja) | 2001-06-19 | 2007-08-01 | 住友金属工業株式会社 | 耐メタルダスティング性を有する金属材料 |
US6740291B2 (en) | 2002-05-15 | 2004-05-25 | Haynes International, Inc. | Ni-Cr-Mo alloys resistant to wet process phosphoric acid and chloride-induced localized attack |
US6764646B2 (en) | 2002-06-13 | 2004-07-20 | Haynes International, Inc. | Ni-Cr-Mo-Cu alloys resistant to sulfuric acid and wet process phosphoric acid |
DK1975267T3 (da) | 2006-01-11 | 2013-07-29 | Nippon Steel & Sumitomo Metal Corp | Metalmateriale med fremragende bestandighed over for metal-dusting/højtemperatur-korrosion |
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CN101978082B (zh) * | 2008-03-25 | 2013-09-18 | 新日铁住金株式会社 | Ni基合金 |
JP4656251B1 (ja) * | 2009-09-18 | 2011-03-23 | 住友金属工業株式会社 | Ni基合金材 |
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