method of processing a workpiece to inhibit precipitation of intermetallic compounds

专利摘要:
METHODS FOR PROCESSING ALLOYS A method of processing a workpiece to inhibit precipitation of intermetallic compounds includes at least one of thermomechanically processing and cooling a workpiece, including an austenitic alloy. During at least one thermomechanical work and cooling of the workpiece, the austenitic alloy is at temperatures in a temperature range that includes the temperature immediately below a calculated solvus sigma temperature of the austenitic alloy below a cooling temperature during a time not exceeding a critical cooling time.
公开号:BR112015008461B1
申请号:R112015008461-3
申请日:2014-02-03
公开日:2021-01-19
发明作者:Robin M. Forbes Jones；Erin T. Mcdevitt
申请人:Ati Properties Llc；
IPC主号:

专利说明:

TECHNOLOGY FOUNDATION TECHNOLOGY FIELD
[001] The present invention relates to alloying methods. The present methods can find application in, for example, and without limitation, the chemical, mining, oil and gas industries. DESCRIPTION OF THE BASIS OF TECHNOLOGY
[002] Metal alloy parts used in chemical processing facilities may be in contact with highly corrosive and / or erosive compounds in demanding conditions. These conditions can subject parts in metal alloys to high stresses and aggressively promote corrosion and erosion, for example. If it is necessary to replace worn, corroded or metallic parts of the chemical processing equipment, it may be necessary to suspend the operations of the facilities for a period of time. Therefore, extending the service life of metal alloy parts used in chemical processing facilities can reduce the cost of the product. The service life can be extended, for example, by improving the mechanical properties and / or corrosion resistance of the alloys.
[003] Likewise, in oil and gas drilling operations, components of the drilling column may degrade due to mechanical, chemical and / or environmental conditions. The components of the drill string can be subjected to impact, abrasion, friction, heat, wear, erosion, corrosion and / or deposits. Conventional alloys may suffer from one or more limitations that impact their usefulness as components of the drill string. For example, conventional materials may lack sufficient mechanical properties (for example, yield strength, tensile strength and / or fatigue resistance), have insufficient corrosion resistance (for example, pitting resistance and / or stress corrosion) , or lack necessary non-magnetic properties. In addition, the properties of conventional alloys can limit the size and possible shape of the drill string components made from the alloys. These limitations can shorten component life, complicating and increasing the cost of drilling for oil and gas.
[004] High-strength non-magnetic stainless steels often contain intermetallic precipitates that decrease the corrosion resistance of the alloys. Galvanic corrosion cells that develop between intermetallic precipitates and the base alloy can significantly decrease the corrosion resistance of non-magnetic high-strength stainless steel alloys used in oil and gas drilling operations.
[005] The broad chemical composition of a non-magnetic high-strength austenitic stainless steel, intended for production exploration and drilling applications in the oil and gas industry is disclosed in the copending US patent application 13 / 331,135, filed on December 20 2011, which is incorporated herein by reference in its entirety. It has been found that the forged parts microstructures of some of the steels described in ‘order 135’ may include intermetallic precipitates. Intermetallic precipitates are believed to be o-phase precipitates, consisting of Fe-Cr-Ni intermetallic compounds. Phase precipitates may compromise the corrosion resistance of stainless steels revealed in 'order135', which may adversely affect the suitability of steels for use in certain aggressive drilling environments. SUMMARY
[006] According to a non-limiting aspect of the present invention, a method of processing a workpiece to inhibit precipitation of intermetallic compounds comprises at least one of thermomechanical work and cooling of a workpiece including an austenitic alloy. During at least one thermomechanical work and cooling of the workpiece, the austenitic alloy is at temperatures in a temperature range that includes the temperature immediately below a calculated solvus sigma temperature of the austenitic alloy below a cooling temperature for a period time not exceeding a critical cooling time. The calculated solvus sigma temperature is a function of the composition of the austenitic alloy in weight percentages and is equal to 1155.8 - (760.4) ^ (nickel / iron) + (1409) ^ (chrome / iron) + (2391.6) ^ (molybdenum / iron) - (288.9) ^ (manganese / iron) - (634.8) ^ (cobalt / iron) + (107.8) ^ (tungsten / iron). The cooling temperature is a function of the composition of the austenitic alloy in weight percentages and is equal to 1290.7 - (604.2) ^ (nickel / iron) + (829.6) ^ (chrome / iron) + (1899 , 6) ^ (molybdenum / iron) - (635.5) ^ (cobalt / iron) + (1251.3) ^ (tungsten / iron). The critical cooling time is a function of the composition of the austenitic alloy in weight percentages and is equal to log10 2,948 + (3,631) ^ (nickel / iron) - (4,846) ^ (chrome / iron) - (11,157) ^ ( molybdenum / iron) + (3.457) ^ (cobalt / iron) - (6.74) ^ (tungsten / iron).
[007] In certain non-limiting modalities of the method, thermomechanically working the part involves forging the part. Such forging may comprise, for example, at least one of roller forging, forging between dies, balanced rotation without roughing, forging with a hammer-pestle, forging with a closed pattern, pressing forging, automatic hot forging, radial forging, and axial compression forging. In certain non-limiting modalities of the method, the critical cooling time is in an interval of 10 minutes to 30 minutes, greater than 10 minutes, or greater than 30 minutes.
[008] In certain non-limiting modalities of the method, after at least one of thermomechanical work and the cooling of the workpiece, the workpiece is heated to an annealing temperature that is at least as large as the calculated solvus sigma temperature , and keeping the workpiece at the annealing temperature for a period of time sufficient to anneal the workpiece. As the workpiece cools from the annealing temperature, the austenitic alloy is at temperatures in a temperature range that includes a temperature slightly less than the solvus sigma temperature calculated for the cooling temperature for a period not exceeding at a critical cooling time.
[009] According to another non-limiting aspect of the present invention, a method of processing an austenitic alloy workpiece to inhibit precipitation of intermetallic compounds comprises forging the workpiece, cooling the forged workpiece, and optionally , annealing the cooled part. During the forging of the workpiece and the cooling of the forged workpiece, the austenitic alloy cools through a temperature range that includes the temperature immediately below a calculated solvus sigma temperature of the austenitic alloy to a cooling temperature over a period of time. time no longer than a critical cooling time. The calculated solvus sigma temperature is a function of the composition of the austenitic alloy in weight percentages and is equal to 1155.8 - (760.4) ^ (nickel / iron) + (1409) ^ (chrome / iron) + (2391.6) ^ (molybdenum / iron) - (288.9) ^ (manganese / iron) - (634.8) ^ (cobalt / iron) + (107.8) ^ (tungsten / iron). The cooling temperature is a function of the composition of the austenitic alloy in weight percentages and is equal to 1290.7 - (604.2) ^ (nickel / iron) + (829.6) ^ (chrome / iron) + (1899 , 6) ^ (molybdenum / iron) - (635.5) ^ (cobalt / iron) + (1251.3) ^ (tungsten / iron). The critical cooling time is a function of the composition of the austenitic alloy in weight percentages and is equal to log10 2,948 + (3,631) ^ (nickel / iron) - (4,846) ^ (chrome / iron) - (11,157) ^ ( molybdenum / iron) + (3.457) ^ (cobalt / iron) - (6.74) ^ (tungsten / iron). In certain non-limiting modalities, forging the part comprises at least one of forging by rollers, forging between prints, balanced rotation without roughing, forging with a hammer and pestle, forging with a closed pattern, forging by pressing, automatic hot forging, radial forging, and axial compression forging.
[010] In certain non-limiting modalities of the method, forging the workpiece occurs entirely at temperatures above the calculated solvus sigma temperature. In certain other non-limiting modalities of the method, forging the part occurs through the calculated solvus sigma temperature. In certain non-limiting modalities of the method, the cooling time is critical in an interval from 10 minutes to 30 minutes, greater than 10 minutes and greater than 30 minutes. BRIEF DESCRIPTION OF THE DRAWINGS
[011] The characteristics and advantages of the device and the methods described here can be better understood by reference to the accompanying drawings, in which:
[012] FIG. 1 is a micrograph showing deleterious intermetallic precipitates in the microstructure at the medium radius of a radial forged workpiece of a non-magnetic austenitic alloy;
[013] FIG. 2 is an isothermal transformation curve or TTT curve predicting the kinetics for 0.1 weight percent of intermetallic precipitation of phase o in an alloy;
[014] FIG. 3 is a graph showing the calculated part center temperature, calculated center temperature, the calculated surface temperature, and the actual temperatures derived from the radial forging of experimental parts from austenitic alloys according to the methods of the present invention;
[015] FIG. 4 is a TTT curve, associated with temperatures and forming and cooling times, according to the modalities of the present invention;
[016] FIG. 5 is a schematic illustration of a non-limiting modality of a process according to the present invention for the production of specific diameter shapes of a high-strength non-magnetic steel useful for exploration and production drilling applications in the oil and gas industry. ;
[017] FIG. 6 is a TTT diagram for an alloy modality having a relatively short critical cooling time as calculated according to an embodiment of the present invention;
[018] FIG. 7 is a micrograph of a central region of a 9-inch diameter workpiece as forged produced using an actual cooling time longer than the calculated critical cooling time required to avoid sigma phase intermetallic precipitation in accordance with the present disclosure;
[019] FIG. 8 is a TTT diagram for an alloy modality having a relatively long critical cooling time as calculated according to an embodiment of the present invention;
[020] FIG. 9 is a micrograph showing the microstructure of the average radius of a 9-inch diameter workpiece as forged using an actual cooling time less than the critical cooling time calculated to prevent sigma phase intermetallic precipitation in accordance with the present disclosure;
[021] FIG. 10 is a graph of temperature versus distance from the back wall of a gradient oven for heat treatments used in Example 3 of the present disclosure;
[022] FIG. 11 is a TTT diagram plotting sampling temperature gradients (horizontal lines) and critical cooling times (vertical lines) used in Example 3 of the present disclosure;
[023] FIG. 12 is a figure superimposing microstructures of the samples maintained for 12 minutes at various temperatures in a TTT diagram for Example 3 of the present disclosure;
[024] FIG. 13 is a figure superimposing microstructures for samples held at 1080 ° F for various times on a TTT diagram for Example 3 of the present disclosure;
[025] FIG. 14A is a micrograph showing the microstructure of a surface region of an alloy of Example 4 of the present disclosure that has been annealed and cooled within the critical cooling time calculated in accordance with the present invention and is devoid of sigma phase precipitates;
[026] FIG. 14B is a micrograph showing the microstructure to a center region of an alloy of Example 4 of the present disclosure that has been annealed, but does not cool within the critical cooling time calculated in accordance with the present disclosure and has sigma phase precipitates;
[027] FIG. 15A is a micrograph showing the microstructure of a surface region of an alloy of Example 5 of the present disclosure that has been forged and cooled within the critical cooling time calculated in accordance with the present invention and is devoid of sigma phase precipitates;
[028] FIG. 15B is a micrograph showing the microstructure to a center region of an alloy of Example 5 of the present disclosure that has been forged and cooled within the critical cooling time calculated in accordance with the present invention and is devoid of sigma phase precipitates;
[029] FIG. 16A is a micrograph showing the microstructure at an average radius of an alloy of Example 6 of the present description that has been forged and cooled for a time that has exceeded the critical cooling time calculated in accordance with the present disclosure and has precipitates in sigma phase in the grain outlines;
[030] FIG. 16B is a micrograph showing the microstructure at an average radius of an alloy of Example 6 of the present description that has been forged and cooled for a time within the critical cooling time calculated in accordance with the present disclosure and does not exhibit sigma phase precipitates in grain outlines;
[031] FIG. 17A is a micrograph showing the microstructure of a surface region of an alloy of Example 7 of the present disclosure that has been forged and cooled for a time within the critical cooling time calculated in accordance with the present description and then hot worked without displaying precipitated in the sigma phase precipitates in the grain boundaries; and
[032] FIG. 17B is a micrograph showing the microstructure of a center region of an alloy of Example 7 of the present disclosure that was forged and cooled during a time within the critical cooling time calculated in accordance with the present description and then hot worked without displaying precipitates of sigma phase in the grain boundaries.
[033] The reader will appreciate the previous details, as well as others, when considering the following detailed description of certain non-limiting modalities in accordance with the present disclosure. DETAILED DESCRIPTION OF CERTAIN NON-LIMITATIVE MODALITIES
[034] It should be understood that the descriptions of certain modalities described here have been simplified to illustrate only those elements, characteristics and aspects that are relevant to a clear understanding of the disclosed modalities, while simultaneously eliminating, for purposes of clarity, other elements, characteristics and aspects . People with knowledge of the technique, upon examination of the present description of the disclosed modalities, will recognize that other elements and / or characteristics may be desirable in a particular implementation or application of the disclosed modalities. However, because these other elements and / or characteristics can be easily determined and applied by experts in the art when considering the present description of the disclosed modalities, and are therefore not necessary for a complete understanding of the disclosed modalities, a description of such elements and / or resources is not provided here. As such, it should be understood that the description presented here is merely exemplary and illustrative of disclosed modalities and is not intended to limit the scope of the invention as defined solely by the claims.
[035] In addition, any numerical range mentioned here is intended to include all the sub-ranges included therein. For example, a range from “1 to 10” is intended to include all sub-ranges between (and inclusive) the minimum value of 1 mentioned and the maximum value of 10, that is, having a minimum value equal to or greater than that 1 and a maximum value of equal to or less than 10. Any maximum numerical limitation mentioned herein is intended to include all of the lower numerical limits included herein and any minimum numerical limitation mentioned here is intended to include all of the higher numerical limits included herein. Accordingly, the Claimants reserve the right to change the present disclosure, including the claims, to expressly mention any sub-ranges subsumed within the ranges expressly cited herein. All of these ranges are intended to be inherently disclosed herein so that you change to expressly mention those sub-ranges that meet the requirements of 35 U.S.C. § 112, first paragraph, and 35 U.S.C. § 132 (a).
[036] The grammatical articles "one", "one", "one", and "o", as used herein, are intended to include "at least one" or "one or more", unless otherwise specified. Thus, articles are used here to refer to one or more of one (that is, at least one) of the grammatical objects of the article. As an example, “a component” means one or more components, and therefore possibly more than one component is contemplated and can be used or employed in an implementation of the described modalities.
[037] All percentages and proportions are calculated based on the total weight of the alloy composition, unless otherwise stated.
[038] Any patent, publication, or other disclosure material that is said to be incorporated, in whole or in part, by reference is incorporated here only insofar as the incorporated material does not conflict with existing definitions, statements or other disclosure material set out in this disclosure. As such, and to the extent necessary, the disclosure as set forth herein replaces any conflicting material incorporated herein by reference. Any material, or part of it, that is said to be incorporated by reference, but which conflicts with the existing definitions, statements, or other disclosure material set forth herein is only incorporated to the extent that there is no conflict between that incorporated material and the existing promotional material.
[039] The present invention includes the description of several modalities. It should be understood that all the modalities described here are exemplary, illustrative, and not limiting. Thus, the invention is not limited by the description of the various exemplary, illustrative, and not limiting modalities. Instead, the invention is defined only by the claims, which can be changed to mention any features expressly or intrinsically described or otherwise expressly or intrinsically supported by the present disclosure.
[040] As used herein, the terms “conformation”, “forging”, and “radial forging” refer to forms of thermomechanical transformation (“TMP”), which can also be referred to here as “thermomechanical work” . Thermo-mechanical work is defined here as generally covering a variety of metal forming processes that combine controlled heat and deformation treatments to obtain synergistic effects, such as improved strength, without loss of strength. This definition of thermomechanical work is consistent with the meaning given in, for example, ASM Materials Engineering Dictionary, J.R. Davis, ed., ASM International (1992), p. 480.
[041] Conventional alloys used in chemical processing, mining and / or oil and gas applications may not have an ideal level of corrosion resistance and / or an ideal level of one or more mechanical properties. Various modalities of processed alloys as discussed herein can have certain advantages over conventional alloys, including, but not limited to, improved corrosion resistance and / or mechanical properties. Certain modalities of alloys processed as described herein can exhibit one or more improved mechanical properties, without any reduction in corrosion resistance, for example. Certain modalities may exhibit improved impact properties, weldability, resistance to corrosion fatigue, resistance to roughness, and / or resistance to brittleness due to the action of hydrogen in relation to certain conventional alloys.
[042] In various embodiments, alloys processed as described here may exhibit increased corrosion resistance and / or advantageous mechanical properties suitable for use in demanding applications. Without wishing to be bound by any particular theory, it is believed that some of the alloys processed as described here may have a higher tensile strength, for example, due to a better response to deformation hardening from deformation, while maintaining a high resistance to corrosion. Hardening by deformation or cold working can be used to harden materials that do not normally respond well to thermal processing. A person skilled in the art, however, will appreciate that the exact nature of the cold-worked structure may depend on the material, applied deformation, deformation rate and / or the deformation temperature. Without wishing to be bound by any particular theory, it is believed that hardening by alloy deformation having the composition described here can more efficiently produce an alloy that has better corrosion resistance and / or mechanical properties than certain alloys conventional.
[043] In certain non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises, consists essentially of, or consists of, chromium, cobalt, copper, iron, manganese, molybdenum, nickel , carbon, nitrogen, tungsten and accidental impurities. In certain non-limiting embodiments, the austenitic alloy may, but need not, include one or more of aluminum, silicon, titanium, boron, phosphorus, sulfur, niobium, tantalum, ruthenium, vanadium, zirconium and, as well as trace elements or as impurities accidental.
[044] Furthermore, according to various non-limiting modalities, the composition of an austenitic alloy transformed by a method of the present invention comprises, consists essentially of, or consists of, percentages by weight based on the total weight of the alloy, up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0 chromium, 15.0 to 38.0 nickel, 2.0 to 9.0 molybdenum , 0.1 to 3.0 copper, 0.08 to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium, up to 0 , 05 boron, up to 0.05 phosphorus, up to 0.05 sulfur, iron and accidental impurities.
[045] In addition, according to various non-limiting modalities, the composition of an austenitic alloy processed by a method according to the present invention comprises, consists essentially of, or consists of, percentages by weight based on the weight of the alloy total up to 0.05 carbon, 1.0 to 9.0 manganese, 0.1 to 1.0 silicon, 18.0 to 26.0 chromium, 19.0 to 37.0 nickel, 3, 0 to 7.0 molybdenum, 0.4 to 2.5 copper, 0.1 to 0.55 nitrogen, 0.2 to 3.0 tungsten, 0.8 to 3.5 cobalt, up to 0.6 titanium, a combined weight percentage of niobium and tantalum not greater than 0.3, up to 0.2 vanadium, up to 0.1 aluminum, up to 0.05 boron, up to 0.05 phosphorus , up to 0.05 sulfur, iron and accidental impurities.
[046] Furthermore, according to various non-limiting modalities, the composition of an austenitic alloy processed by a method according to the present invention may comprise, consist essentially of, or consist of, weight percentages based on the total weight alloy, up to 0.05 carbon, 2.0 to 8.0 manganese, 0.1 to 0.5 silicon, 19.0 to 25.0 chromium, 20.0 to 35.0 nickel , 3.0 to 6.5 molybdenum, 0.5 to 2.0 copper, 0.2 to 0.5 nitrogen, 0.3 to 2.5 tungsten, 1.0 to 3.5 cobalt , up to 0.6 titanium, a combined weight percentage of niobium and tantalum not exceeding 0.3, up to 0.2 vanadium, up to 0.1 aluminum, up to 0.05 boron, up to 0.05% phosphorus, up to 0.05 sulfur, iron and accidental impurities.
[047] In various non-limiting modalities, the composition of an auscultitic alloy processed by a method according to the present invention comprises carbon in any of the following weight percentage ranges: up to 2.0; up to 0.8; up to 0.2; up to 0.08; up to 0.05; up to 0.03; 0.005 to 2.0; 0.01 to 2.0; 0.01 to 1.0; 0.01 to 0.8; 0.01 to 0.08; 0.01 to 0.05; and 0.005 to 0.01.
[048] In various non-limiting modalities, the composition of an alloy according to the present disclosure can comprise manganese, in any of the following weight percentage ranges: up to 20.0; up to 10.0; 1.0 to 20.0; 1.0 to 10; 1.0 to 9.0; 2.0 to 8.0; 2.0 to 7.0; 2.0 to 6.0; 3.5 to 6.5; and from 4.0 to 6.0.
[049] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises silicon in any of the following weight percentage ranges: up to 1.0; 0.1 to 1.0; 0.5 to 1.0; and 0.1 to 0.5.
[050] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises chromium in any of the following weight percent ranges: 14.0 to 28.0; 16.0 to 25.0; 18.0 to 26; 19.0 to 25.0; 20.0 to 24.0; 20.0 to 22.0; 21.0 to 23.0; and 17.0 to 21.0.
[051] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises nickel in any of the following weight percentage ranges: 15.0 to 38.0; 19.0 to 37.0; 20.0 to 35.0; and 21.0 to 32.0.
[052] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises molybdenum in any of the following weight percentage ranges: 2.0 to 9.0; 3.0 to 7.0; 3.0 to 6.5; 5.5 to 6.5; and 6.0 to 6.5.
[053] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises copper, in any of the following weight percentage ranges: 0.1 to 3.0; 0.4 to 2.5; 0.5 to 2.0; and 1.0 to 1.5.
[054] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises nitrogen in any of the following weight percentage ranges: 0.08 to 0.9; 0.08 to 0.3; 0.1 to 0.55; 0.2 to 0.5; and from 0.2 to 0.3. In certain embodiments, nitrogen in the austenitic alloy can be limited to 0.35 percent by weight or 0.3 percent by weight to address its limited solubility in the alloy.
[055] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises tungsten in any of the following weight percentage ranges: 0.1 to 5.0; 0.1 to 1.0; 0.2 to 3.0; 0.2 to 0.8; and 0.3 to 2.5.
[056] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises cobalt in any of the following weight percent ranges: up to 5.0; 0.5 to 5.0; 0.5 to 1.0; 0.8 to 3.5; 1.0 to 4.0; 1.0 to 3.5; and 1.0 to 3.0. In certain embodiments, cobalt unexpectedly improved the mechanical properties of the alloy. For example, in certain alloy modalities, cobalt additions can provide up to a 20% increase in strength, up to a 20% increase in elongation, and / or improved corrosion resistance. Without wishing to be bound by any particular theory, it is believed that the substitution of iron with cobalt may increase the resistance to the formation of precipitation in deleterious sigma phase in the alloy after hot forming in relation to the non-cobalt containing variants that showed levels higher sigma phase in grain contours after hot forming.
[057] In several non-limiting modalities, the composition of an austenitic alloy processed by a method according to the invention comprises a weight ratio of cobalt / tungsten from 2: 1 to 5: 1, or 2 : 1 to 4: 1. In certain embodiments, for example, the weight percentage of cobalt / tungsten can be about 4: 1. The use of cobalt and tungsten can strengthen the solid solution of the alloy.
[058] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises titanium in any of the following weight percent ranges: up to 1.0; up to 0.6; up to 0.1; up to 0.01; 0.005 to 1.0; and 0.1 to 0.6.
[059] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises zirconium in any of the following weight percentage ranges: up to 1.0; up to 0.6; up to 0.1; up to 0.01; 0.005 to 1.0; and 0.1 to 0.6.
[060] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises niobium and / or tantalum in any of the following weight percentage ranges: up to 1.0; up to 0.5; up to 0.3; 0.01 to 1.0; 0.01 to 0.5; 0.01 to 0.1; and 0.1 to 0.5.
[061] In various non-limiting modalities, the composition of an austenitic alloy processed by a method according to the present invention comprises a combined weight percentage of niobium and tantalum, in any of the following ranges: up to 1.0; up to 0.5; up to 0.3; 0.01 to 1.0; 0.01 to 0.5; 0.01 to 0.1; and 0.1 to 0.5.
[062] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises vanadium in any of the following weight percentage ranges: up to 1.0; up to 0.5; up to 0.2; 0.01 to 1.0; 0.01 to 0.5; 0.05 to 0.2; and 0.1 to 0.5.
[063] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises aluminum in any of the following weight percentage ranges: up to 1.0; up to 0.5; up to 0.1; up to 0.01; 0.01 to 1.0; 0.1 to 0.5; and 0.05 to 0.1.
[064] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises boron, in any of the following weight percentage ranges: up to 0.05; up to 0.01; up to 0.008; up to 0.001; up to 0.0005.
[065] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises phosphorus in any of the following weight percentage ranges: up to 0.05; up to 0.025; up to 0.01; and up to 0.005.
[066] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises sulfur in any of the following weight percentage ranges: up to 0.05; up to 0.025; up to 0.01; and up to 0.005.
[067] In various non-limiting embodiments, the balance of the composition of an austenitic alloy according to the present invention may comprise, consist essentially of, or consist of, iron and accidental impurities. In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises iron in any of the following weight percent ranges: up to 60; up to 50; 20 to 60; 20 to 50; 20 to 45; 35 to 45; 30 to 50; 40 to 60; 40 to 50; 40 to 45; and 50 to 60.
[068] In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises one or more trace elements. As used herein, “trace elements” refers to elements that may be present in the alloy, as a result of the composition of the raw materials and / or the method of fusion employed and that are present in concentrations that do not negatively affect the properties significantly important elements of the alloy, since these properties are generally described here. Trace elements can include, for example, one or more of titanium, zirconium, niobium, tantalum, vanadium, aluminum and boron in any of the concentrations described herein. In certain non-limiting modalities, trace elements may not be present in alloys in accordance with the present disclosure. As is known in the art, in the production of alloys, trace elements can typically be largely or entirely eliminated by selecting certain starting materials and / or using certain processing techniques. In various non-limiting embodiments, the composition of an austenitic alloy according to the present invention can comprise a total concentration of trace elements in any of the following weight percent ranges: up to 5.0; up to 1.0; up to 0.5; up to 0.1; 0.1 to 5.0; 0.1 to 1.0; and 0.1 to 0.5.
[069] In various non-limiting modalities, the composition of an austenitic alloy processed by a method according to the present invention comprises a total concentration of accidental impurities, in any of the following weight percentage ranges: up to 5.0 ; up to 1.0; up to 0.5; up to 0.1; 0.1 to 5.0; 0.1 to 1.0; and 0.1 to 0.5. As used herein, the term "accidental impurities" refers to elements present in the alloy, in lower concentrations. Such elements may include one or more of bismuth, calcium, cerium, lanthanum, lead, oxygen, phosphorus, ruthenium, silver, selenium, sulfur, tellurium, tin and zirconium. In various non-limiting modalities, individual accidental impurities in the composition of an austenitic alloy processed in accordance with the present disclosure do not exceed the following maximum percentages by weight: 0.0005 bismuth; 0.1 calcium; 0.1 cerium; 0.1 lanthanum; 0.001 lead; 0.01 tin, 0.01 oxygen; 0.5 ruthenium; 0.0005 silver; 0.0005 selenium; and 0.0005 tellurium. In various non-limiting embodiments, the composition of an auspicious alloy processed by a method according to the present invention, the combined weight percentage of cerium, lanthanum, and the presence of calcium in the alloy (if present) can be up to 0.1. In various non-limiting embodiments, the combined weight percentage of cerium and / or lanthanum present in the composition of an austenitic alloy can be up to 0.1. Other elements that may be present as accidental impurities in the composition of austenitic alloys processed as described herein, will be apparent to those skilled in the art. In various non-limiting embodiments, the composition of an austenitic alloy processed by a method according to the present invention comprises a total concentration of trace elements and accidental impurities, in any of the following weight percentage ranges: up to 10.0; up to 5.0; up to 1.0; up to 0.5; up to 0.1; 0.1 to 10.0; 0.1 to 5.0; 0.1 to 1.0; and 0.1 to 0.5.
[070] In various non-limiting embodiments, an austenitic alloy processed according to a method of the present invention may be non-magnetic. This feature can facilitate the use of the alloy in applications where non-magnetic properties are important. Such applications include, for example, certain applications of oil and gas drilling column components. Certain non-limiting modalities of the processed austenitic alloy as described herein, can be characterized by a magnetic permeability value (Dr) within a given range. In various non-limiting embodiments, the magnetic permeability value of an alloy processed in accordance with the present disclosure can be less than 1.01, less than 1.005, and / or less than 1.001. In various embodiments, the alloy can be substantially free of ferrite.
[071] In various non-limiting embodiments, an austenitic alloy processed by a method according to the present invention can be characterized by an equivalent number of pitting resistance (PREN) within a given range. As is understood, PREN assigns a value relative to the expected resistance of an alloy to pitting corrosion in an environment with chloride. Generally, alloys that have a higher PREN are expected to have better corrosion resistance than alloys that have a lower PREN. A particular PREN calculation provides a PREN 16 value using the following formula, where the percentages are weight percentages based on the total weight of the alloy: PREN16 =% Cr + 3.3 (% Mo) + 16 (% N) + 1.65 (% W) In various non-limiting embodiments, an alloy processed using a method according to the present invention can have a PREN 16 value in any of the following ranges: up to 60; up to 58; greater than 30; greater than 40; greater than 45; greater than 48; 30 to 60; 30 to 58; 30 to 50; 40 to 60; 40 to 58; 40 to 50; and 48 to 51. Without intending to link to any particular theory, it is believed that a higher PREN16 value may indicate a greater probability that the alloy will show sufficient resistance to corrosion in environments such as, for example, in highly corrosive environments , which may exist in, for example, chemical processing equipment and for the downhole environment to which the drilling column is subjected in oil and gas drilling applications. Aggressively corrosive environments can subject, for example, alkaline compounds, acidified chloride solutions, acidified sulfide solutions, peroxides, and / or CO2, together with extreme temperatures.
[072] In several non-limiting modalities, an austenitic alloy processed by a method according to the present invention can be characterized by a sensitivity coefficient to avoid precipitation value (CP) within a certain range. The concept of a CP value is described in, for example, US Patent 5,494,636, entitled “Austenitic Stainless Steel Having High Properties”. In general, the CP value is a relative indication of the precipitation kinetics of intermetallic phases in an alloy. A CP value can be calculated using the following formula, where the percentages are percentages by weight based on the total weight of the alloy: CP = 20 (% Cr) + 0.3 (% Ni) + 30 (% Mo) + 5 (% W) + 10 (% Mn) + 50 (% C) - 200 (% N) Without wishing to be bound by any particular theory, it is believed that alloys that have a CP value of less than 710 will show austenite stability advantageous that helps to minimize HAZ (heat affected zone) sensitization of intermetallic phases during welding. In various non-limiting modalities, an alloy processed as described herein can have a CP in any of the following ranges: up to 800; up to 750; less than 750; up to 710; less than 710; up to 680; and 660 to 750.
[073] In various non-limiting embodiments, an austenitic alloy according to the present invention can be characterized by a critical pitting corrosion temperature (CPT) and / or a critical crevice corrosion temperature (CCCT) within particular ranges. In certain applications, CPT and CCCT values can more accurately indicate the corrosion resistance of an alloy than the PREN value. CPT and CCCT can be measured according to ASTM G48 to 11, entitled “Standard Test Methods for Pitting and Crevice Corrosion Resistance of Stainless Steels and Related Alloys by Use of Ferric Chloride Solution”. In various non-limiting embodiments, the CPT of an alloy processed in accordance with the present invention can be at least 45 ° C, or more preferably at least 50 ° C, and CCCT can be at least 25 ° C, or more preferably at least 30 ° C.
[074] In various non-limiting embodiments, an austenitic alloy processed by a method according to the present invention can be characterized by a stress corrosion resistance (SCC) value within a given range. The concept of an SCC value is described in, for example, A. J. Sedricks, Corrosion of Stainless Steels (J. Wiley and Sons 1979). In several non-limiting modalities, the SCC value of an alloy according to the present disclosure can be determined by specific applications, according to one or more of the following procedures: ASTM G30-97 (2009), entitled “Standard Practice for Making and Using U-Bend Stress-Corrosion Test Specimens ”; ASTM standard G36-94 (2006), entitled “Standard Practice for Evaluating Stress-Corrosion-Cracking Resistance of Metals and Alloys in a Boiling Magnesium Chloride Solution”; ASTM standard G39-99 (2011), “Standard Practice for Preparation and Use of Bent-Beam Stress-Corrosion Test Specimens”; ASTM standard G49-85 (2011), “Standard Practice for Preparation and Use of Direct Tension Stress-Corrosion Test Specimens”; and ASTM G123-00 (2011), “Standard Test Method for Evaluating Stress-Corrosion Cracking of Stainless Alloys with Different Nickel Content in Boiling Acidified Sodium Chloride Solution.” In various non-limiting embodiments, the SCC value of an alloy processed in accordance with the present invention is sufficiently high to indicate that the alloy can adequately support boiling point acidified sodium chloride solution for 1000 hours without suffering cracks under deformation corrosion. unacceptable, according to assessment under the ASTM G123-00 (2011) standard.
[075] It has been discovered that the microstructures of forged workpieces of alloy compositions described above can contain deleterious intermetallic precipitates. It is believed that intermetallic precipitates are likely to be sigma phase precipitates, that is, compounds of (Fe, Ni) 3 (Cr, Mo) 2. Intermetallic precipitates can impair the corrosion resistance of the alloys and negatively impact their suitability for oil and gas drilling service and other aggressive environments. FIG. 1 shows an example of harmful intermetallic precipitate 12 in microstructure 10 in the middle radius of a radial forged workpiece. The chemical composition of the alloy shown in FIG. 1 is within the alloy compositions listed here and consisted of, in weight percentages based on the total weight of the alloy: 26.0397 iron; 33.94 nickel; 22.88 chromium; 6.35 molybdenum; 4.5 manganese; 3.35 cobalt; 1.06 tungsten; 1.15 copper; 0.01 niobium; 0.26 silicon; 0.04 vanadium; 0.019 carbon; 0.0386 nitrogen; 0.015 phosphorus; 0.0004 sulfur; and accidental impurities.
[076] If intermetallic precipitates are confined to an alloy surface, surface grinding can be used to remove the deleterious layer containing the intermetallic precipitates, with a concomitant reduction in product yield and increased product costs. In some alloy compositions, however, deleterious intermetallic precipitates can extend significantly inward or across the cross section of a radial forged workpiece, in which case the workpiece may be totally unsuitable for the condition as radial forged for applications subjecting the alloy to, for example, highly corrosive conditions. An option for removing harmful intermetallic precipitates from the microstructure is to treat the radial forged workpiece with a solution before a radial forging operation at cooling temperature. This, however, adds an additional processing step and increases cycle time and cost. In addition, the time it takes to cool the workpiece from the annealing temperature is dependent on the diameter of the workpiece, and must be fast enough to prevent the formation of harmful intermetallic precipitates.
[077] Without wishing to be bound by any particular theory, it is believed that intermetallic precipitates are formed mainly because the precipitation kinetics are fast enough to allow precipitation to occur during the time necessary to form the workpiece. FIG. 2 is an isothermal transformation curve 20, also known as a "TTT diagram" or "TTT curve", which provides the kinetics for phase o 0.1 in percentage weight (sigma phase) of the intermetallic precipitation in the alloy having the above composition described for FIG. 1. It will be seen from FIG. 2 that intermetallic precipitation occurs more quickly, that is, in the shortest time, at the apex 22 or “nose” of the “C” curve, which comprises the isothermal transformation curve 20.
[078] FIG. 3 is a graph showing a combination 30 of a workpiece center temperature 32, calculated average radius temperature 34, calculated surface temperature 36, and the actual radial forging temperatures of experimental austenitic alloy workpieces having the chemical compositions indicated in Table 1. These compositions fall within the scope of the alloy compositions described above in the present detailed description. The workpieces were about 10 inches in diameter, and actual temperatures were measured using optical pyrometers. The nose temperature of the TTT diagram is represented as line 38. Table 1 also shows the PREN16 values for the listed alloy compositions.

[079] It can be seen from FIG. 3 that the actual surface temperature of the workpieces during radial forging is close to the temperature at which the kinetics of intermetallic precipitation is faster, thus promoting the precipitation of harmful intermetallic compounds.
[080] Using JMatPro thermodynamic modeling software, available from Sente Software Ltd., Surrey, UK, relationships were determined between the content of specific elements in certain alloys described here and (1) the time to the peak of the curve. isothermal transformation and (2) the temperature in the apex area of the isothermal transformation curve. It was determined that the adjustment of the levels of various elements of the alloys can alter the time for the apex of the isothermal transformation curve and, thus, allow the thermomechanical processing that occurs without the formation of deleterious intermetallic precipitates. Examples of thermomechanical processing that can be applied include, among others, radial forging and press forging.
[081] As a consequence, a non-limiting aspect of the present disclosure is directed to a quantitative relationship discovered between the chemical composition of a non-magnetic high-strength austenitic steel and the maximum time allowed for processing the alloy as it cools between a strip specific temperature in order to avoid the formation of harmful intermetallic precipitates in the alloy. FIG. 4 is a TTT curve 48, showing a calculated solvus sigma temperature 42, a cooling temperature 44, and a critical cooling time 50, and also illustrates a relationship 40 according to the present disclosure that defines the maximum time or time or critical cooling 50 allowed processing of the alloy as it cools within a specific temperature range to prevent precipitation of harmful intermetallic compounds.
[082] The relationship 40 illustrated in FIG. 4 can be described using three equations. Equation 1 defines the calculated solvus sigma temperature, shown in FIG. 4 per line 42. Equation 1 Calculated Sigma Solvus Temperature (° F) = 1155.8 - [(760.4H% nickel /% iron)] + [(1409) ^ (% chromium /% iron)] + [(2391 , 6) ^ (% molybdenum /% iron)] - [(288.9) '(% manganese /% iron) - [(634.8)' (% cobalt /% iron)] + [(107.8) '(% tungsten /% iron)]. When austenitic steels, in accordance with the present disclosure, are equal to or higher than the solvus sigma temperature calculated in accordance with Equation 1, deleterious intermetallic precipitates did not form in the alloys.
[083] In a non-limiting mode, the workpiece is thermomechanically processed at a temperature in a thermomechanical processing temperature range. The temperature range is from a temperature just below the calculated solvus sigma temperature 42 of the austenitic alloy to a cooling temperature 44 of the austenitic alloy. Equation 2 is used to calculate the cooling temperature 44 in degrees Fahrenheit as a function of the chemical composition of the austenitic steel alloy. With reference to FIG. 4, the cooling temperature 44 calculated according to Equation 2 is intended to predict the temperature of the apex 46 of the isothermal transformation curve 48 of the alloy. Equation 2 Cooling temperature (° F) = 1290.7 - [(604.2H% nickel /% iron)] + [(829.6) '(% chromium /% iron)] + [(1899.6)' (% molybdenum /% iron)] - [(635.5) '(% cobalt /% iron)] + [(1251.3) ^ (% tungsten /% iron)].
[084] Equation 3 is an equation that predicts the time in log10 minutes that vertex 46 of the isothermal transformation curve 48 for the particular alloy occurs. Equation 3 Critical cooling time (logw in minutes) = 2.948 + [(3,631) ^ (% nickel /% iron)] - [(4,846) ^ (% chrome /% iron)] - [(11,157) ^ ( % molybdenum /% iron)] + [(3.457) * (% cobalt /% iron)] - [(6.74) '(% tungsten /% iron)].
[085] With reference to FIG. 4, the moment when the vertex 46 of the isothermal transformation curve 48 occurs is represented by the arrow 50. The time calculated by Equation 3 and represented by the arrow 50 in FIG. 4 is referred to here as the “critical cooling time”. If the time during which the alloy cools in the temperature range that extends to a temperature just below the calculated solvus sigma temperature 42 and the cooling temperature 44 is longer than the critical cooling time 50, deleterious intermetallic precipitates can occur. to form. Intermetallic precipitates may render the alloy or product unsuitable for its intended use because of galvanic corrosion cells established between the intermetallic precipitates and the base alloy. More generally, to prevent the formation of harmful intermetallic precipitates, the time to process the alloy thermomechanically over a temperature range that includes a temperature immediately below the calculated solvus sigma temperature 42 to the cooling temperature 44 should not be greater than critical cooling time 50.
[086] In a non-limiting mode, the part is allowed to cool from a temperature immediately below the calculated solvus sigma temperature 42 and the cooling temperature 44 within a time of no more than the critical cooling time 50. It will be recognized that the workpiece can be allowed to cool during thermomechanical processing of the workpiece. For example, and it should not be limiting, a workpiece can be heated to a temperature in a range of thermomechanical processing temperatures and subsequently processed thermomechanically using a forging process. As the workpiece is thermomechanically processed, the workpiece can cool to a certain degree. In a non-limiting mode, allowing the workpiece to cool comprises the natural cooling that can occur during thermomechanical processing. According to one aspect of the present disclosure, it is only necessary that the time that the workpiece spends in a cooling temperature range that covers a temperature just below the calculated solvus sigma temperature 42 and the cooling temperature 44, is not longer than the critical cooling time 50.
[087] According to certain non-limiting modalities, a critical cooling time that is practical for forging, radial forging, or other thermomechanical processing of an austenitic alloy workpiece according to the present invention is within a range of 10 minutes to 30 minutes. Certain other non-limiting modalities include a critical cooling time of more than 10 minutes, or more than 30 minutes. It will be recognized that, according to the methods of the present invention, the critical cooling time calculated according to equation 3 based on the chemical composition of the alloy is the maximum time allowed to process thermomechanically and / or to cool in a temperature range that includes the temperature immediately lower than the calculated solvus sigma temperature (calculated by Equation 1 above) until the cooling temperature (calculated by Equation 2 above).
[088] The calculated solvus sigma temperature, calculated by Equation 1, and the cooling temperature calculated by Equation 2, define the end points of the temperature range over which the cooling time requirement, or, as stated here, the critical cooling time is important. The time during which the alloy is worked hot or above the calculated solvus sigma temperature, calculated according to Equation 1, is not important for the present method, since the elements that form deleterious intermetallic precipitates treated here remain in solution when the alloy is at or above the calculated solvus sigma temperature. Instead, only the time during which the workpiece is within the temperature range that covers a temperature immediately below the calculated solvus sigma temperature (calculated using Equation 1) for the cooling temperature (calculated using Equation 2) , which is referred to here as the cooling temperature range, is important to prevent deleterious inter-metallic precipitation of phase o. In order to avoid the formation of harmful o-phase intermetallic particles, the actual time that the workpiece spends in the calculated cooling temperature range should not be greater than the critical cooling time calculated as in Equation 3.
[089] In addition, the time during which the workpiece is at a temperature below the cooling temperature calculated in accordance with Equation 2 is not important for the present method because below the cooling temperature, the rates of diffusion of the elements comprising the harmful intermetallic precipitates are low enough to inhibit the substantial formation of the precipitates. The total time it takes to work the alloy at a temperature lower than the solvus sigma temperature calculated according to Equation 1 and then to cool the alloy to the cooling temperature according to equation 2, that is, the time during which the alloy is in the temperature range delimited by (i) a temperature immediately below the calculated solvus sigma temperature and (ii) the cooling temperature, must not be greater than the critical cooling time according to equation 3.
[090] Table 2 shows the calculated solvus sigma temperatures, calculated using equation 1, the cooling temperatures calculated from equation 2, and the critical cooling times calculated from equation 3 for the three alloys that have the compositions in Table 1.

[091] According to a non-limiting aspect of the present disclosure, thermomechanically working a workpiece according to the methods of the present invention comprises forging the workpiece. For the thermomechanical forging process, the thermomechanical working temperature and the thermomechanical working temperature range according to the present disclosure can be referred to as the forging temperature and the forging temperature range, respectively.
[092] According to another aspect of the present disclosure, thermomechanically working a workpiece according to the methods of the present invention may comprise radial forging of the workpiece. For the thermomechanical radial forging process, the thermomechanical processing temperature range according to the present invention can be referred to as the radial forging temperature range.
[093] In a non-limiting embodiment of a method according to the present invention, the step of thermomechanically working or processing the workpiece comprises or consists of forging the alloy. Forging can include, but is not limited to, any of the following types of forging: roller forging, forging between stamping, balanced rotation without roughing, forging with a hammer-pestle, closed die forging, isothermal forging, printing press forging, forging by pressing, automatic hot forging, radial forging, and axial compression forging. In a specific modality, forming comprises or consists of radial forging.
[094] In accordance with a non-limiting aspect of the present disclosure, a workpiece can be annealed after the thermomechanical work and cooling steps in accordance with the present disclosure. Annealing comprises heating the workpiece to a temperature that is equal to or greater than the solvus sigma temperature calculated in accordance with Equation 1, and keeping the workpiece at a temperature for a period of time. The annealed workpiece is then cooled. The cooling of the annealed workpiece in the temperature range that includes the temperature immediately below the calculated solvus sigma temperature (calculated according to Equation 1) and the cooling temperature calculated according to Equation 2 must be completed within the critical cooling calculated according to equation 3, in order to avoid the deleterious intermetallic phase precipitation. In a non-limiting mode, the alloy is annealed in a tempering range from 1900 ° F to 2300 ° F, and the alloy is maintained at the annealing temperature for 10 minutes to 1500 minutes.
[095] It will be recognized that the methods of processing an austenitic alloy workpiece to inhibit the precipitation of intermetallic compounds according to the present invention apply to any and all alloys with chemical compositions described in the present description.
[096] FIG. 5 is a schematic diagram of a process 60, which is a non-limiting embodiment of a method according to the present disclosure. Process 60 can be used to manufacture high strength non-magnetic steel product shapes with diameters useful for production exploration and drilling applications in the oil and gas industry. The material is cast with a 20-inch (62) diameter ingot, using a combination of decarbonisation in oxygen and argon and electro-sludge remelting (AOD / ESR). AOD and ESR are techniques known to those skilled in the art and are therefore not further described here. The 20-inch diameter ingot is radially forged to a 14-inch diameter (64), reheated, and radially forged to about 9 inches in diameter (66). The 9-inch diameter ingot is then allowed to cool (not shown in FIG. 5). The final step of process 60 is a low temperature radial forging operation to reduce the diameter to approximately 7.25 inches in diameter (68). The 7.25-inch diameter rod can be cut several times (70) for polishing, testing and / or further processing.
[097] In the scheme shown in FIG. 5, the steps referring to the method of the present invention are the radial forging step from the workpiece approximately 14 inches in diameter (64) to approximately 9 inches in diameter (66), and the subsequent or simultaneous step, during which the radial forged workpiece cools (not shown in FIG. 5). With reference to FIG. 4, all regions (that is, the entire cross section of the workpiece) of the radial forged workpiece approximately 9 inches in diameter must cool from a temperature just below the calculated solvus sigma temperature 42 and the cooling temperature 44 in a time no longer than the calculated critical cooling time 50. It will be recognized that in certain non-limiting modalities in accordance with the present disclosure, all or a certain amount of cooling to the cooling temperature 44 can occur while the part The workpiece is simultaneously being worked thermomechanically or forged, and the cooling of the workpiece does not need to occur entirely as a separate step from the thermomechanical work step or forging.
[098] During a direct radial forging operation, the fastest cooling occurs on the workpiece surface, and the surface region may end up being processed at or below the cooling temperature 44, as previously described. To prevent precipitation of the harmful intermetallic precipitate, the cooling time of the surface region must comply with the critical cooling time restriction 50 calculated from the alloy composition, using Equation 3.
[099] In a non-limiting mode, it is possible to reduce the available cooling window by adding an additional process step designed to eliminate the intermetallic precipitate from the workpiece as forged. The additional process step can be a heat treatment adapted to dissolve the intermetallic precipitate in the forged workpiece at temperatures higher than the calculated solvus sigma temperature 42. However, any time required for the surface, the average radius, and the center of the workpiece to cool after heat treatment must be within the critical cooling time calculated in accordance with Equation 3. The cooling speed after the step of the additional heat treatment process is partly dependent on the workpiece diameter, with the center cooling of the part at a slower rate. The larger the diameter of the workpiece, the slower the cooling speed of the center of the workpiece. In any case, the cooling between a temperature immediately below the calculated solvus sigma temperature and the calculated cooling temperature should be no more than the critical cooling time in Equation 3.
[0100] An unexpected observation during the development of the present invention was that nitrogen had a significant influence on the time available for processing in which nitrogen suppressed the precipitation of harmful intermetals and thus allowed for more critical cooling times without the formation of compounds harmful intermetallics. Nitrogen, however, is not included in Equations 1 to 3 of the present disclosure, because in a non-limiting modality, nitrogen is added to the austenitic alloys processed according to the present methods at an element solubility limit, which will be relatively constant. over the range of chemical compositions for the austenitic alloys described here.
[0101] After thermomechanically working an austenitic alloy and cooling according to the methods described here and the limitations of Equations 1 to 3, the processed alloy can be manufactured in or included in various articles of manufacture. Manufacturing articles may include, but are not limited to, parts and components for use in the chemical, petrochemical, mining, oil, gas, paper products, food processing, pharmaceutical, and / or water service industries. Non-limiting examples of specific articles of manufacture that may include alloys processed by methods according to the present invention include: a tube; a leaf; a plate; a bar; a rod; a forging; a tank; a pipe component; piping, condensers, and heat exchangers for use with chemicals, gas, oil, seawater, water service, and / or corrosive liquids (eg, alkaline compounds, acidified chloride solutions, acidified sulfide solutions, and / or peroxides); filter washers, vats, and press rolls in cellulose bleaching plants; water piping systems for nuclear power plant services and flue gas purification environments for power plants; components for process systems for oil and gas platforms; gas well components, including tubes, valves, supports, landing nozzles, tool joints, and packers; turbine engine components; desalination components and pumps; distillation and packaging columns for oil and resins; items for marine environments, such as, for example, transformer boxes; valves; transmissions; flanges; reactors; collectors; separators; exchangers; bombs; compressors; fasteners; flexible connectors; bellows; chimney linings; duct components; and certain drill string components, such as, for example, stabilizers, rotatable drillable components, drill collars, integral blade stabilizers, stabilizing mandrels, drill and measurement pipes, measurement boxes during drilling, record boxes during drilling, non-magnetic drilling collars, non-magnetic pipe drill, integral non-magnetic blade stabilizers, flexible non-magnetic collars, and compression service drill pipes.
[0102] In relation to the methods according to the present description, austenitic alloys having the compositions described in the present description can be provided by any suitable conventional technique known in the art for the production of the alloys. Such techniques include, for example, fusion practices and powder metallurgy practices. Non-limiting examples of conventional fusing practices include, but are not limited to, practices using consumable product fusion techniques (for example, vacuum arc remelting (VAR) and ESR, non-consumable fusion techniques (for example, fusion in cold plasma furnace and electron beam cold furnace melting), and a combination of two or more of these techniques. As is known in the art, certain powder metallurgy practices for the preparation of an alloy generally involve the production of powders alloying by the following steps: AOD, decarburization in vacuum oxygen (VOD), or vacuum induction melting (VIM) of ingredients to provide a melt having the desired composition; supplying an alloy powder, and pressing and sintering all or a portion of the alloy powder.In a conventional atomization technique, a stream of the melt is brought into contact with the spinning blade of an atomi user who breaks the chain into small droplets. The droplets can be rapidly solidified in a vacuum or inert gas atmosphere, providing small solid particles from the alloy.
[0103] After thermomechanically working and cooling a workpiece according to the limitations of Equations 1 -3 of the present disclosure, the austenitic alloys described here may have better resistance to corrosion and / or mechanical properties compared to conventional alloys. After thermomechanical work, a workpiece and cooling according to the limitations of Equations 1 to 3 of the present disclosure, non-limiting modalities of the alloys described here may have a tensile strength, yield stress, elongation percentage, and / or superior hardness, comparable to, or better than DATALLOY 2® alloy (UNS not assigned) and / or AL-6XN® alloy (UNS N08367), which are available from Allegheny Technologies Incorporated, Pittsburgh, Pennsylvania USA. . In addition, after thermomechanically processing and allowing the workpiece to cool according to the limitations of Equations 1 to 3 of the present disclosure, the alloys described herein may have comparable or better PREN, CP, CPT, CCCT, and / or SCC values than DATALLOY 2® and / or AL-6XN® alloy. In addition, after thermomechanically processing and allowing the workpiece to cool according to the limitations of Equations 1 to 3 of the present disclosure, the alloys described here may have better resistance to fatigue, microstructural stability, toughness, resistance to thermal cracking, pitting corrosion, galvanic corrosion, SCC, machinability, and / or roughness resistance in relation to DATALLOY 2® alloy and / or AL-6XN® alloy. DATALLOY 2® alloy is a Cr-Mn-N stainless steel alloy with the following nominal composition, in weight percentages: 0.03 carbon; 0.30 silicon; 15.1 manganese; 15.3 chromium; 2.1 molybdenum; 2.3 nickel; 0.4 nitrogen; balance of iron and impurities. AL-6XN® alloy is a superaustenitic stainless steel alloy having the following typical composition, in weight percentages: 0.02 carbon; 0.40 of manganese; 0.020 phosphorus; 0.001 sulfur; 20.5 chromium; 24.0 nickel; 6.2 molybdenum; 0.22 nitrogen; 0.2 copper; balance of iron and impurities.
[0104] In certain non-limiting modalities, after cooling and thermomechanical work of a workpiece according to the limitations of Equations 1 to 3 of the present disclosure, the alloys described here may have, at room temperature, the tensile strength of minus 110 Ksi, yield stress of at least 50 ksi, and / or elongation percentage of at least 15%. In several other non-limiting modalities, after forming, forging, or radial forging and cooling in accordance with the present description, the alloys described here can exhibit, in the annealed state and at room temperature, the tensile strength in the range of 90 Ksi to 150 Ksi, yield stress in the range of 50 ksi to 120 ksi, and / or elongation percentage in the range of 20% to 65%.
[0105] The following examples are intended to further describe certain non-limiting modalities, without restricting the scope of this disclosure. Those skilled in the art will appreciate that the variations of the following examples are possible within the scope of the invention, which is defined only by the claims. EXAMPLE 1
[0106] FIG. 6 shows an example of a TTT 80 diagram for an alloy that has a relatively short allowable critical cooling time as calculated using Equation 3 of the present disclosure. The chemical composition of the alloy which is the object of FIG. 6 includes, in weight percentages: 26.04 iron; 33.94 nickel; 22.88 chromium; 6.35 molybdenum; 4.5 manganese; 3.35 cobalt; 1.06 tungsten; 1.15 copper; 0.01 niobium; 0.26 silicon; 0.04 vanadium; 0.019 carbon; 0.386 nitrogen; 0.015 phosphorus; and 0.0004 sulfur. For this alloy composition, the calculated solvus sigma temperature 82 calculated in accordance with Equation 1 of the present description is about 1859 ° F; the cooling temperature 84 calculated according to Equation 2 of the present description is about 1665 ° F; and the critical cooling time 86 calculated according to equation 3 of the present description is about 7.5 minutes. According to the present disclosure, in order to avoid precipitation of the harmful intermetallic phase, the workpiece must be thermomechanically processed and allowed to cool when the temperature within the range of just below 1859 ° F (ie the solvus sigma temperature calculated, calculated by Equation 1) up to 1665 ° F (ie, the cooling temperature calculated according to Equation 2) for no more than 7.5 minutes (that is, the critical cooling time calculated according to the equation 3).
[0107] FIG. 7 shows the center microstructure of a 9-inch diameter workpiece as forged having the Racing 48FJ composition as revealed in Table 1. The 9-inch workpiece was made as follows. A 20 inch diameter electro-slag remelted (ESR) ingot was homogenized at 2225 ° F, reheated to 2150 ° F, hot worked in a radial forging to a piece of approximately 14 inches and cooled in air. The 14-inch workpiece was reheated to 2200 ° F and hot worked in a radial forging for a workpiece about 9 inches in diameter, followed by quenching in water. The actual actual cooling time, that is, the time to forge and then cool within the temperature range immediately below the calculated 1859 ° F solvus sigma temperature, calculated by Equation 1 up to the 1665 ° F cooling temperature calculated by the equation 2, was greater than 7.5 minutes of critical cooling time calculated by Equation 3 allowed to avoid sigma phase intermetallic precipitation. As predicted from Equations 1 to 3, the micrograph of FIG. 7 shows that the microstructure of the workpiece forged as a 9-inch diameter contained deleterious intermetallic precipitates, most likely sigma, in the grain contours. EXAMPLE 2
[0108] FIG. 8 shows an example of a TTT 90 diagram for an alloy that has a more critical cooling time calculated using Equation 3 than the alloy of FIG. 6. The chemical composition of the alloy of FIG. 8 is composed, in weight percentages: 39.78 of iron; 25.43 nickel; 20.91 chromium; 4.78 molybdenum; 4.47 of manganese; 2.06 cobalt; 0.64 tungsten; 1.27 copper; 0.01 niobium; 0.24 silicon; 0.04 vanadium; 0.0070 carbon; 0.37 nitrogen; 0.015 phosphorus; and 0.0004 sulfur. The calculated solvus sigma temperature 92 for the alloy calculated according to Equation 1 is about 1634 ° F; the cooling temperature 94 calculated according to Equation 2 is about 1556 ° F; and the critical cooling time 96 calculated according to equation 3 is about 28.3 minutes. According to the method of the present disclosure, in order to avoid precipitation of the harmful intermetallic phase within the alloy, the alloy must be formed and cooled when in the temperature range that covers a temperature immediately below the calculated solvus sigma temperature (1634 ° F ) to the calculated cooling temperature (1556 ° F) for a time not exceeding the calculated critical cooling time (28.3 minutes).
[0109] FIG. 9 shows the medium radius microstructure of a 9 inch diameter workpiece as forged from the alloy. The workpiece was made as follows. An alloy ingot about 20 inches in diameter ESR from the alloy was homogenized at 2225 ° F, hot worked in a radial forging for a workpiece about 14 inches in diameter and air cooled. The cooled part was reheated to 2200 ° F and hot worked in a radial forging to a work piece about 10 inches in diameter, followed by quenching in water. The relevant actual cooling time, that is, the forging and cooling time, while in the temperature range that covers a temperature immediately below the calculated solvus sigma temperature, calculated according to Equation 1 (1634 ° F) until the temperature cooling time calculated according to Equation 2 (1556 ° F), was less than the critical cooling time calculated according to Equation 3 (28.3 minutes) allowed to avoid the sigma phase intermetallic precipitation. As predicted from equations 1 to 3, the micrograph of FIG. 9 shows that the microstructure of the workpiece as forged 9 inches in diameter did not contain deleterious intermetallic precipitates of sigma phase in the grain contours. The darkened areas in the grain boundaries are attributed to engraved metallographic artifacts and do not represent precipitates at the grain boundary. EXAMPLE 3
[0110] Samples of the non-magnetic austenitic alloy of Race number 49FJ were provided (see Table 1). The alloy had a calculated solvus sigma temperature, calculated according to Equation 1 of 1694 ° F. Cooling temperature of the alloy calculated according to Equation 2 is 1600 ° F. The time for the nose of curve C of the TTT diagram (that is, the critical cooling time) calculated according to equation 3 was 15.6 minutes. The alloy samples were calcined at 1950 ° F for 0.5 hours. The annealed samples were placed in a gradient oven with the back wall of the oven at about 1600 ° F, the front wall of the oven at approximately 1000 ° F, and a temperature gradient inside the intermediate oven between the front and rear wall. The temperature gradient in the oven is reflected in the graph shown in FIG. 10. The samples were placed in locations inside the oven so as to be subjected to temperatures of 1080 ° F, 1200 ° F, 1300 ° F, 1400 ° F, 1500 ° F, or 1550 ° F, and were heated for 12 minutes, 50 minutes, 10 hours, or 20 hours. The microstructure of each sample was evaluated at the particular heating temperature applied to the sample.
[0111] FIG. 11 is a TTT diagram with the heating temperature gradients (horizontal lines) and the actual cooling times (vertical lines) that were used in these experiments. FIG. 12 superimposes microstructures of the samples kept for 12 minutes at different temperatures in the TTT diagram. FIG. 13 superimposes microstructures of samples maintained at 1080 ° F several times on the TTT diagram. In general, the results confirm the accuracy of the TTT diagrams in which precipitation of the intermetallic phase treated here occurred approximately at the temperatures and times defined by the TTT diagram. EXAMPLE 4
[0112] A 20-inch ESR diameter ingot with Race 48FJ chemistry was provided. The alloy had a calculated solvus sigma temperature, calculated using Equation 1 of 1851 ° F. The cooling temperature calculated according to Equation 2 was 1659 ° F. The time for the nose of curve C of the TTT diagram (that is, the critical cooling time) calculated according to equation 3 was 8.0 minutes. The ESR ingot was homogenized at 2225 ° F, reheated to 2225 ° F and hot worked in a radial forging for a workpiece about 14 inches in diameter, and then cooled by air. The cooled 14-inch diameter workpiece was reheated to 2225 ° F and hot worked in a radial forging for a workpiece about 10 inches in diameter, followed by water quenching. Optical temperature measurements during the radial forging operation indicated that the surface temperature was approximately 1778 ° F, and as the workpiece was radially forged it entered the water quench tank, the surface temperature was about 1778 ° F. The radial forged and water quenched workpiece was annealed at 2150 ° F and then quenched in water.
[0113] FIG. 14A shows the microstructure on the surface of the annealed radial forged workpiece. FIG. 14B shows the microstructure in the center of the annealed radial forged workpiece. The 2150 ° F annealing step solves the sigma phase that was formed during the radial forging operation. The calculated critical cooling time of 8.0 minutes, however, is insufficient to prevent the formation of a sigma phase in the center of the ingot as the ingot cools from a temperature slightly below the calculated solvus sigma temperature of 1851 ° F to cooling temperature 1659 ° F calculated during the quenching operation in water. The micrograph of FIG. 14A shows that the cooled surface quickly enough prevents sigma phase precipitation, but the micrograph of FIG. 14B shows that the cooling in the center of the ingot occurred slowly enough to allow sigma phase precipitation. The center of the ingot cooled from the calculated solvus sigma temperature, calculated by Equation 1 and the cooling temperature calculated by Equation 2 over a period of time longer than the critical cooling time calculated by Equation 3. EXAMPLE 5
[0114] A 20-inch diameter ESR ingot with Race 45FJ chemistry was provided. The alloy had a calculated solvus sigma temperature, calculated using Equation 1 of 1624 ° F. The cooling temperature calculated according to Equation 2 was 1561 ° F. The nose time for curve C in the TTT diagram (ie, the critical cooling time) was 30.4 minutes. The ESR ingot was homogenized at 2225 ° F, reheated to 2225 ° F and hot worked in a radial forge for a piece about 14 inches in diameter, and then cooled by air. The workpiece was reheated to 2225 ° F and hot worked in a radial forging for a workpiece about 10 inches in diameter, followed by quenching in water. Optical temperature measurements during the radial forging operation indicated that the surface temperature of the workpiece was approximately 1886 ° F, and as the radial forged workpiece entered the water quench tank, the surface temperature was about 1790 ° F.
[0115] FIG. 15A shows the microstructure of the surface of the radial forged workpiece and quenched in water. FIG. 15B shows the microstructure in the center of the radial forged workpiece and quenched in water. The microstructures shown in both FIG. 15A and FIG. 15B are devoid of sigma precipitation. This confirms that the actual time to cool from a temperature just below the calculated solvus sigma temperature of 1624 ° F to the calculated cooling temperature of 1561 ° F was fast enough (ie less than 30.4 minutes), to avoid sigma phase precipitation, on both the surface and the center of the radial forged workpiece and quenched in water. EXAMPLE 6
[0116] A 20-inch diameter ESR ingot with Race 48FJ chemistry was provided. The Racing 48FJ alloy had a calculated solvus sigma temperature, calculated using Equation 1 of 1851 ° F. The cooling temperature calculated according to Equation 2 was 1659 ° F. The time for the nose of curve C of the TTT diagram (that is, the critical cooling time) calculated according to equation 3 was 8.0 minutes. A second ESR ingot 20 inches in diameter, having the 49FJ Race chemistry, was provided. The Racing 49FJ alloy had a calculated solvus sigma temperature, calculated using Equation 1 of 1694 ° F. The cooling temperature calculated according to Equation 2 was 1600 ° F. The time for the nose of curve C of the TTT diagram (that is, the critical cooling time) calculated according to equation 3 was 15.6 minutes.
[0117] The two ingots were homogenized at 2225 ° F. The homogenized ingots were reheated to 2225 ° F and hot worked in a radial forging for workpieces about 14 inches in diameter, followed by air cooling. Both chilled workpieces were reheated to 2225 ° F and hot worked in a radial forging for workpieces about 10 inches in diameter, followed by water quenching.
[0118] Optical temperature measurements during the radial forging operation of the Running 48FJ ingot indicated that the surface temperature was approximately 1877 ° F, and when entering the water quench tank, the surface temperature was about 1778 ° F. FIG. 16A shows the center microstructure of the alloy, which included sigma phase precipitate at the grain boundary.
[0119] The optical temperature measurements during the radial forging operation of the Running 49FJ ingot indicated that the surface temperature was approximately 1848 ° F, and when entering the water tempering tank the surface temperature was around 1757 ° F. FIG. 16B shows the microstructure of the center of the alloy, which is devoid of sigma phase precipitates. The dark regions in the grain outlines in the micrograph of FIG. 16B are assigned to metallographic engraving artifacts.
[0120] These results demonstrate that even when processed under essentially identical conditions, the workpiece with the shortest critical cooling time as calculated by Equation 3 (Race 48FJ) developed a sigma phase at its center, while the workpiece with the longer critical cooling time (Race 49FJ) as calculated by Equation 3 did not develop a sigma phase precipitate at its center. EXAMPLE 7
[0121] A 20-inch diameter ESR ingot with Race 49FJ chemistry was provided. The Racing 49FJ alloy had a calculated solvus sigma temperature, calculated using Equation 1 of 1694 ° F. The cooling temperature calculated according to Equation 2 was 1600 ° F. The time for the nose of curve C of the TTT diagram (that is, the critical cooling time) calculated according to equation 3 was 15.6 minutes. The ingot was homogenized at 2225 ° F, reheated to 2225 ° F and hot worked in a radial forging for a workpiece about 14 inches in diameter, and then cooled by air. The air-cooled workpiece was reheated to 2150 ° F and hot worked in a radial forging for a workpiece about 9 inches in diameter, followed by water quenching. Optical temperature measurements during the radial forging operation indicated that the surface temperature was approximately 1800 ° F, and as the radial forged workpiece entered the water quench tank, the surface temperature was around 1700 ° F. The workpiece forged and quenched in water was then reheated to 1025 ° F and hot worked in a radial forging for a workpiece about 7.25 inches in diameter, followed by air cooling.
[0122] The microstructure of the 7.25 inch diameter workpiece surface is shown in FIG. 17A, and the microstructure of the 7.25-inch diameter workpiece center is shown in FIG. 17B. The micrographs show that there was no sigma phase formation on any surface or the center of the workpiece. In this example, the workpiece with 49FJ Racing chemistry was processed through the relevant temperature range, that is, the temperature range limited by a temperature immediately below the calculated solvus sigma temperature and the calculated cooling temperature, in less than than the calculated critical cooling time, thus avoiding sigma phase precipitation.
[0123] It should be understood that the present description illustrates those aspects of the invention relevant to a clear understanding of the invention. Certain aspects that would be evident to those skilled in the art and that, therefore, would not facilitate a better understanding of the present invention have not been presented in order to simplify the present description. Although only a limited number of modalities of the present invention are necessarily described herein, one skilled in the art, in considering the foregoing description, recognizes that many modifications and variations of the invention can be employed. All such variations and modifications of the present invention are intended to be covered by the foregoing description and the following claims.

权利要求:
Claims (26)
[0001]
1. Method of processing a workpiece to inhibit the precipitation of intermetallic compounds, the method comprising: at least one among working thermomechanically and cooling a workpiece including an austenitic alloy, in which, for at least one among thermomechanical work and cooling of the workpiece, the austenitic alloy is at temperatures in a temperature range that includes the temperature just below the calculated solvus sigma temperature of the austenitic alloy to a cooling temperature for no longer than one critical cooling time; where the austenitic alloy consists of, in weight percentages based on the total weight of the alloy, up to 0.2 carbon, up to 20 manganese, 0.1 to 1.0 silicon, 14.0 to 28.0% chromium, 15.0 to 38.0 nickel, 2.0 to 9.0 molybdenum, 0.1 to 3.0 copper, 0.08 to 0.9 nitrogen, 0.1 to 5.0 tungsten, 0.5 to 5.0 cobalt, up to 1.0 titanium, a combined weight percentage of niobium and tantalum not exceeding 0.3, up to 0.2 of vanadium; up to 0.1 aluminum, up to 0.05 boron; up to 0.05 phosphorus; up to 0.05 sulfur; iron; and accidental impurities, the method CHARACTERIZED by the fact that: the calculated solvus sigma temperature is a function of the composition of the austenitic alloy in weight percentages and, in degrees Fahrenheit, is equal to 1155.8 - (760.4) ^ (nickel / iron) + (1409) ^ (chrome / iron) + (2391.6) * (molybdenum / iron) - (288.9) ^ (manganese / iron) - (634.8) ^ (cobalt / iron) + (107.8) ^ (tungsten / iron); the cooling temperature is a function of the composition of the austenitic alloy in weight percentages and, in degrees Fahrenheit, is equal to 1290.7 - (604.2) ^ (nickel / iron) + (829.6) ^ ( chromium / iron) + (1899.6) ^ (molybdenum / iron) - (635.5) ^ (cobalt / iron) + (1251.3) * (tungsten / iron); and the critical cooling time is a function of the composition of the austenitic alloy in weight percentages and, in minutes, is equal to log10 2,948 + (3,631) * (nickel / iron) - (4,846) ^ (chrome / iron ) - (11,157) «(molybdenum / iron) + (3,457)« (cobalt / iron) - (6,74) ^ (tungsten / iron).
[0002]
2. Method, according to claim 1, CHARACTERIZED by the fact that thermomechanically working the workpiece comprises forging the workpiece.
[0003]
3. Method, according to claim 2, CHARACTERIZED by the fact that forging the workpiece comprises at least one of the forging by rolls, forging between dies, balanced rotation without roughing, forging with hammer-pestle, forging with closed print, pressing forging, automatic hot forging, radial forging, and axial compression forging.
[0004]
4. Method, according to claim 1, CHARACTERIZED by the fact that the critical cooling time is in a range of 10 minutes to 30 minutes.
[0005]
5. Method, according to claim 1, CHARACTERIZED by the fact that the critical cooling time is more than 30 minutes.
[0006]
6. Method, according to claim 1, CHARACTERIZED by the fact that it also comprises, after at least one of thermomechanically working and cooling the workpiece: heat the workpiece to an annealing temperature that is at least as great how the calculated solvus sigma temperature, and keeping the workpiece at the annealing temperature for a period of time sufficient to anneal the workpiece; where as the workpiece cools from the annealing temperature, the austenitic alloy is at temperatures in a temperature range that includes the temperature immediately below the calculated solvus sigma temperature up to the cooling temperature for a time not exceeding a critical cooling time.
[0007]
7. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy comprises a combined weight percentage of cerium and lanthanum not exceeding 0.1.
[0008]
8. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy comprises up to 0.5 weight percent ruthenium.
[0009]
9. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy comprises up to 0.6 weight percent of zirconium.
[0010]
10. Method according to claim 1, CHARACTERIZED by the fact that the austenitic alloy comprises up to 60 weight percent iron.
[0011]
11. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy is non-magnetic.
[0012]
12. Method according to claim 1, CHARACTERIZED by the fact that the austenitic alloy has a magnetic permeability value of less than 1.01 H / m.
[0013]
13. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy consists of, in weight percentages based on the total weight of the alloy: up to 0.05 carbon; 1.0 to 9.0 manganese; 0.1 to 1.0 silicon; 18.0 to 26.0 chromium; 19.0 to 37.0 nickel; 3.0 to 7.0 molybdenum; 0.4 to 2.5 copper; 0.1 to 0.55 nitrogen; 0.2 to 3.0 tungsten; 0.8 to 3.5 cobalt; up to 0.6 titanium; a combined weight percentage of niobium and tantalum not exceeding 0.3; up to 0.2 vanadium; up to 0.1 aluminum; up to 0.05 boron; up to 0.05 phosphorus; up to 0.05 sulfur; iron; and accidental impurities.
[0014]
14. Method according to claim 13, CHARACTERIZED by the fact that the austenitic alloy comprises 2.0 to 8.0 weight percent of manganese.
[0015]
15. Method, according to claim 13, CHARACTERIZED by the fact that the austenitic alloy comprises 19.0 to 25.0 weight percent chromium.
[0016]
16. Method according to claim 13, CHARACTERIZED by the fact that the austenitic alloy comprises 20.0 to 35.0 weight percent nickel.
[0017]
17. Method according to claim 13, CHARACTERIZED by the fact that the austenitic alloy comprises 3.0 to 6.5 weight percent molybdenum.
[0018]
18. Method according to claim 13, CHARACTERIZED by the fact that the austenitic alloy comprises 20 to 50 weight percent iron.
[0019]
19. Method, according to claim 1, CHARACTERIZED by the fact that the austenitic alloy consists of, in weight percentages based on the total weight of the alloy: up to 0.05 carbon; 2.0 to 8.0 manganese; 0.1 to 0.5 silicon; 19.0 to 25.0 chromium; 20.0 to 35.0 nickel; 3.0 to 6.5 molybdenum; 0.5 to 2.0 copper; 0.2 to 0.5 nitrogen; 0.3 to 2.5 tungsten; 1.0 to 3.5 cobalt; up to 0.6 titanium; a combined weight percentage of niobium and tantalum not exceeding 0.3; up to 0.2 vanadium; up to 0.1 aluminum; up to 0.05 boron; up to 0.05 phosphorus; up to 0.05 sulfur; iron; trace elements; and accidental impurities.
[0020]
20. Method, according to claim 19, CHARACTERIZED by the fact that the austenitic alloy comprises 2.0 to 6.0 weight percent of manganese.
[0021]
21. Method according to claim 19, CHARACTERIZED by the fact that the austenitic alloy comprises 20.0 to 22.0 weight percent chromium.
[0022]
22. Method according to claim 19, CHARACTERIZED by the fact that the austenitic alloy comprises 6.0 to 6.5 weight percent molybdenum.
[0023]
23. Method, according to claim 1, CHARACTERIZED by the fact that thermomechanically working the workpiece comprises forging the workpiece; and optionally anneal the cooled workpiece.
[0024]
24. Method, according to claim 23, CHARACTERIZED by the fact that the workpiece forging takes place entirely at temperatures above the calculated solvus sigma temperature.
[0025]
25. Method, according to claim 23, CHARACTERIZED by the fact that the forging of the workpiece occurs through the calculated solvus sigma temperature.
[0026]
26. Method, according to claim 23, CHARACTERIZED by the fact that the forging of the workpiece comprises at least one of forging by rollers, forging between dies, balanced rotation without roughing, forging with hammer and pestle, forging with closed print , press forging, automatic hot forging, radial forging, and axial compression forging.

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法律状态:
2017-10-03| B25D| Requested change of name of applicant approved|Owner name: ATI PROPERTIES LLC (US) |

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2018-11-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-09| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-03-24| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-17| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-01-19| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/02/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/777,066|US9869003B2|2013-02-26|2013-02-26|Methods for processing alloys|

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US13/777,066|2013-02-26|

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PCT/US2014/014405|WO2014133718A1|2013-02-26|2014-02-03|Methods for processing alloys|

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