WO2008064214A1 - Filler metal composition and method for overlaying low nox power boiler tubes - Google Patents
Filler metal composition and method for overlaying low nox power boiler tubes Download PDFInfo
- Publication number
- WO2008064214A1 WO2008064214A1 PCT/US2007/085217 US2007085217W WO2008064214A1 WO 2008064214 A1 WO2008064214 A1 WO 2008064214A1 US 2007085217 W US2007085217 W US 2007085217W WO 2008064214 A1 WO2008064214 A1 WO 2008064214A1
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- WIPO (PCT)
- Prior art keywords
- alloy
- boiler
- weight
- weld
- overlay
- Prior art date
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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
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
-
- 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
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/1266—O, S, or organic compound in metal component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12937—Co- or Ni-base component next to Fe-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12861—Group VIII or IB metal-base component
- Y10T428/12944—Ni-base component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
Definitions
- the present invention relates to a nickel, chromium, iron, aluminum, niobium, titanium welding alloy, articles made therefrom for use in producing weldments, and weldments and methods for producing these weldments.
- the present invention relates to Ni- Cr alloys useful as weld overlays applied for the purpose of enhancing corrosion resistance and, more particularly, where corrosion resistance in his temperature sulfidizing-oxidizing environments is a life-limiting factor.
- weld overlays are required to provide long-term corrosion resistance including resistance to corrosion fatigue cracking.
- the types of resistance requirements include sulfidation, carburization and coal ash corrosion resistance over a range of temperatures of 700 0 F through 145O 0 F, which includes service in ultra- supercritical environments.
- boiler waterwalls Prior to the initiation of NOx (oxides of nitrogen) control, boiler waterwalls did not require weld overlay and performed well when low alloy steels containing small amounts of chromium and sometimes molybdenum were used. Likewise, high-carbon austenitic stainless steel superheater and reheater tubes often performed well before the advent of low NOx boilers.
- weld overlays to be used was the molybdenum-free, nickel- chromium alloys that contained between 30-44% chromium.
- Superheater and reheater tubes seem to be performing well with 40-44% chromium-balance nickel overlays even in slightly reducing, carburizing and sulfidizing environments created by "supertuning".
- waterwall tubes exposed to sulfidation in lower partial pressures of oxygen required greater protection during the most heavily reducing burn times.
- the present invention improves upon the current 40-44% chromium-balance nickel materials via additions of aluminum in the range of 0.5% to 2,0% and niobium in the range of up to 2%, in the interest of providing additional enhancements to corrosion resistance while maintaining the same degree of fabricability and usability as currently available materials.
- the alloy material of the invention is expected to find application for environments requiring resistance to metal dusting corrosion as well. Applications associated with production of syngas, consisting primarily of hydrogen and carbon monoxide, will be of primary interest.
- the present invention overcomes the limitations of the prior art by providing a nickel, chromium, iron, niobium, titanium, aluminum welding alloy and weldments made therefrom that provide the desired corrosion resistance in addition to resistance to hot cracking, as well as corrosion fatigue cracking.
- the present invention further provides a welding alloy of the nickel, chromium, iron, titanium, aluminum type that is particularly adapted for use in fabricating equipment used in low NOx, coal-fired power generation.
- a further object of the invention is to provide a welding alloy of the nickel, chromium, aluminum type that is particularly adapted to fabricating and overlaying equipment, such as tubes, used in low NOx coal-fired power boilers.
- a nickel, chromium, iron, titanium, aluminum alloy for use in producing weld deposits.
- the alloy comprises, in weight percent, about 36-43% chromium, about 0.5-2.0% aluminum, about 0-2.0% Nb, about 0- 1.0% Mo, about 0.2-5.0% iron, about 0.3-1.0% titanium, about 0.005-0.05% carbon, less than 0.50% silicon, preferably 0.10-0.30% silicon, less than 0.01% sulfur, less than 0.02% phosphorus, about 0.005-0.020% magnesium plus calcium and the balance substantially nickel and incidental impurities.
- the alloy exhibits adequate corrosion resistance in view of the chromium and aluminum content.
- the alloy may be in the form of a weld deposit, a welding electrode, a welding electrode in the form of a wire with a flux cover, a welding electrode in the form of a sheath with a flux core, a weld deposit overlay or a weldment comprising an alloy substrate, such as steel with an overlay of the alloy of the invention. It may be used in a method for producing a weld deposit or weldment in the form of a flux-covered electrode used for producing a weld deposit that includes welding performed by submerged arc welding or electroslag welding.
- the weldment may be in the form of weld-overlaid superheater, reheater, or waterwall tubes of a fossil fuel-fired power generation boiler.
- the method for producing the weld deposit may include producing a flux-covered electrode of a nickel, chromium wire, or a nickel, chromium, iron wire and melting the electrode to produce a weld deposit.
- FIG. 1 is a graph showing depth of attack after exposure in simulated low-NOx boiler environment with alternating oxidizing-sulfidizing and oxidizing cycles for alloys of the present invention and comparative alloys;
- FIG. 2 is a phase stability diagram prediction for alloy A of the present invention
- FIG. 3 is a phase stability diagram prediction for alloy B of the present invention
- FIG. 4 is a phase stability diagram prediction for alloy C of the present invention
- FIG. 5 is a phase stability diagram prediction for alloy D of the present invention
- FIG. 6 is a phase stability diagram prediction for alloy 1 of the present invention
- FIG. 7 is a graph showing measured room temperature electrical resistivity values in the as- welded and 1000°F/4940h aged conditions for weld overlays fabricated on carbon steel using alloys 1 , 2, A 5 B and C; and
- FIG. 8 is a graph showing interpolated room temperature thermal conductivity values in the as- welded and 1000°F/4940h aged conditions for weld overlays fabricated on carbon steel using alloys 1, 2, A, B and C.
- NiCrFeAlNbTi welding alloy in accordance with the invention has sufficient chromium and aluminum along with tight control of secondary and trace elements to provide suitable corrosion resistance to sulfidation, carburization, and coal ash conditions as well as resistance to corrosion fatigue.
- the alloy has good weldability and resistance to solidification cracking during welding.
- the alloy should have adequate solubility for its alloying elements and a narrow Hquidus to solidus temperature range. Also, it should have low levels of sulfur, phosphorus, and other low-melting elements and it should contain minimum levels of elements that form low-melting point phases in the alloy. Because the very high chromium content challenges the limit of solubility in nickel, careful control of sulfur, magnesium and calcium is required for solidification cracking resistance, also.
- Table I shows the composition of the alloys in the present invention that have been exposed to laboratory corrosion testing in which conditions were varied from oxidizing- sulfidiziiig (4 days per cycle) to oxidizing (3 days per cycle) at 100O 0 F.
- Table II shows the composition of alloys tested which lie outside the present invention.
- Table III shows the gaseous constituents of the environments to which the samples were exposed.
- Figure 1 compares depth of attack as a function of time up to a total testing duration of 4940 hours. With the exception of alloy 2, all materials were tested in the form of weld overlays. Weld deposits were made onto carbon steel using the Gas Tungsten Arc Welding (GTAW) process. Note that corrosion rates were lowest among the high chromium- containing nickel alloys and very lowest among the alloys containing the highest Al level. Alloys A, B 5 C and D of the present invention exhibit improved performance over the others tested. Figures 2 through 6 show phase diagram predictions for these alloys, in addition to alloy 1, performed using JmatPro ® by Sente Software.
- GTAW Gas Tungsten Arc Welding
- Figure 7 shows electrical resistivity values at room temperature for alloys 1 , 2, A, B and C. Alloys 1 , A, B and C exhibit much lower electrical resistivity than alloy 2, which is currently used for application of weld overlays in low-NOx boiler waterwalls. As electrical resistivity is known to be inversely proportional to thermal conductivity, lowering of electrical resistivity should result in a commensurate increase in thermal conductivity.
- Figure 8 shows interpolated thermal conductivity values, based upon the electrical resistivity values shown in Figure 7, and known values of electrical resistivity and thermal conductivity for a range of nickel-base materials. This characteristic could be advantageous for an overlay material, as the surface temperature in service would be effectively lower and the boiler could operate more efficiently by virtue of improved heat transfer across the boiler tube wall.
- This improved thermal conductivity would offer several advantages when the alloy is used as an overlay. Because corrosion rate is usually proportional to surface temperature, higher thermal conductivity would allow superheated steam to be produced at the design temperature while the overlay surface operated at lower temperature than that of corresponding tubes overlaid with materials of lower thermal conductivity. At the same time, higher thermal conductivity of the overlay provides for higher overall boiler thermal efficiency.
- the high-chromium nickel alloys of 36-43% Cr perform satisfactorily in environments that contain more than a partial pressure of about 10 "38 atmosphere partial pressure of oxygen, typical of a conventional coal-fired boiler but not likely present beneath the coal ash of a low NO x boiler.
- the high chromium nickel alloys heretofore used develop less protective oxide scales that have been found to exhibit reduced sulfidation resistance.
- the alloy of the present invention shows that with a small addition of about 0.5% to 2% Al, the protection afforded by the known high chromium nickel alloys can be extended to environments exhibiting even lower partial pressures of oxygen as is present beneath the coal ash found to coat typical coal-fired boiler tubes. See Table IV, below. [0029] TABLE IV
- Mass change data (mg/cm 2 ) and depth of attack (inches) after 4940 hours at 538 0 C in a simulated flue gas environment alternating 4 days reducing (67% N 2 - 16% CO 2 - 5% CO - 10% H 2 O - 2% H 2 S) and 3 days oxidizing (72% N 2 - 71.2% CO 2 - 10.8% H 2 O).
- thermal conductivity of these alloys as weld overlays has been found to increase with time as the result of the precipitation of alpha chromium and the onset of a nickel-chromium ordering reaction.
- This enhancement of thermal conductivity improves the overall efficiency of the coal-fired power plant resulting in benefits to power providers, their customers and even the environment.
- the enhancement of the thermal conductivity over time under service conditions at 538 0 C is presented in Table V, below.
- the as-deposited overlay hardness allows for tube bending and field fabrication.
- the ordering and alpha chromium precipitation reactions that occur at the typical surface temperatures found on the waterwall, superheater and reheater boiler tubing increase the hardness of the weld overlay and thus provide improved erosion resistance for the boiler tubing, as reported below in Table VI.
- the hot workability of the alloy range has been improved by the use of a Mg and Ca deoxidation treatment as described in U.S. Patent No. 6,106,643 to Suarez et al. [0033] TABLE VI
- the alloy of the present invention provides a weld overlay alloy for boiler tubes having enhanced coal-ash corrosion resistance under extreme reducing conditions, coupled with increasing thermal conductivity and hardness with time at service temperature in a coal-fired, low NOx boiler environment.
- the welding alloy of the invention may be deposited on the boiler tubes by a spiral overlaying technique which in itself is well-known in the art.
- This technique may utilize a conventional integrated robotic overlay application system employing a plurality of full function robots, power supplies and microprocessor controller hardware to provide consistent weld metal deposition of uniform thickness.
- the spiral overlaid tubing can be post- weld bent to most any desired boiler layout configuration.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Arc Welding In General (AREA)
- Nonmetallic Welding Materials (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR20097010963A KR101512202B1 (en) | 2006-11-21 | 2007-11-20 | FILLER METAL COMPOSITION AND METHOD FOR OVERLAYING LOW N0x POWER BOILER TUBES |
JP2009538487A JP5420417B2 (en) | 2006-11-21 | 2007-11-20 | Filler composition and method for low NOx power boiler tube overlay |
CN200780043204.1A CN101583731B (en) | 2006-11-21 | 2007-11-20 | Filler metal composition and method for overlaying low NOx power boiler tubes |
EP07864654.4A EP2121996B1 (en) | 2006-11-21 | 2007-11-20 | Filler metal composition and method for overlaying low nox power boiler tubes |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US86032106P | 2006-11-21 | 2006-11-21 | |
US60/860,321 | 2006-11-21 | ||
US11/942,252 US8568901B2 (en) | 2006-11-21 | 2007-11-19 | Filler metal composition and method for overlaying low NOx power boiler tubes |
US11/942,252 | 2007-11-19 |
Publications (1)
Publication Number | Publication Date |
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WO2008064214A1 true WO2008064214A1 (en) | 2008-05-29 |
Family
ID=39166820
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2007/085217 WO2008064214A1 (en) | 2006-11-21 | 2007-11-20 | Filler metal composition and method for overlaying low nox power boiler tubes |
Country Status (6)
Country | Link |
---|---|
US (1) | US8568901B2 (en) |
EP (1) | EP2121996B1 (en) |
JP (1) | JP5420417B2 (en) |
KR (1) | KR101512202B1 (en) |
CN (1) | CN101583731B (en) |
WO (1) | WO2008064214A1 (en) |
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EP2992985A1 (en) * | 2014-09-05 | 2016-03-09 | Ametek, Inc. | Nickel-chromium alloy and method of making the same |
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US20150275341A1 (en) | 2012-10-11 | 2015-10-01 | Scoperta, Inc. | Non-magnetic metal alloy compositions and applications |
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2007
- 2007-11-19 US US11/942,252 patent/US8568901B2/en active Active
- 2007-11-20 JP JP2009538487A patent/JP5420417B2/en active Active
- 2007-11-20 WO PCT/US2007/085217 patent/WO2008064214A1/en active Application Filing
- 2007-11-20 CN CN200780043204.1A patent/CN101583731B/en active Active
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- 2007-11-20 EP EP07864654.4A patent/EP2121996B1/en active Active
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2992985A1 (en) * | 2014-09-05 | 2016-03-09 | Ametek, Inc. | Nickel-chromium alloy and method of making the same |
CN105420553A (en) * | 2014-09-05 | 2016-03-23 | 埃米特克有限公司 | Nickel-Chromium Alloy And Method Of Making The Same |
EP3563948A1 (en) * | 2014-09-05 | 2019-11-06 | Ametek, Inc. | Nickel-chromium alloy and method of making the same |
US11130201B2 (en) | 2014-09-05 | 2021-09-28 | Ametek, Inc. | Nickel-chromium alloy and method of making the same |
Also Published As
Publication number | Publication date |
---|---|
EP2121996B1 (en) | 2017-11-15 |
CN101583731B (en) | 2014-08-13 |
JP5420417B2 (en) | 2014-02-19 |
EP2121996A1 (en) | 2009-11-25 |
CN101583731A (en) | 2009-11-18 |
KR101512202B1 (en) | 2015-04-14 |
US8568901B2 (en) | 2013-10-29 |
US20080241580A1 (en) | 2008-10-02 |
JP2010510074A (en) | 2010-04-02 |
KR20090094435A (en) | 2009-09-07 |
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