AUSTENITIC ALLOYS BASED ON IRON-MANGANESE AND IRON-MANGANESE-CHROMIUM

Abstract: Manganese-iron base and manganese-chromium-iron base austenitic alloys designed to have resistance to neutron irradiation induced swelling and low activation have the following compositions (in weight percent): 20 to 40 Mn; 0 to 15 Cr; 0.4 to 3.0 Si; an austenite stabilizing element selected from C and N, alone or in combination with each other, and in an amount effective to substantially stabilize the austenite phase, but less than 0.7 C, and less than 0.3 N; 0 to 2.5 V; 0 to 0.1 P; 0 to 0.01 B; 0 to 3.0 Al; 0 to 0.5 Ni; 0 to 2.0 W; 0 to 1.0 Ti; 0 to 1.0 Ta; and with the remainder of the alloy being essentially iron.

Description: MANGANESE-IRON BASE AND MANGANESE-CHROMIUM-IRON BASE AUSTENITIC ALLOYS This invention relates to manganese-iron base and manganese-chromium-iron base austenitic alloys. It is especially concerned with those alloys having resistance to neutron irradiation induced swelling and low post irradiation residual radioactivity (i.e. low activation). Over the years, a number of austenitic, nickelchromium-iron base, alloys and ferritic, chromium-iron base, alloys have been studied and developed for use in the high temperature, high energy neutron (0*1 MeV to 1.0 MeV) environment encountered in a liquid metal fast breeder reactor (LMFBR) -- a fission reactor. One of the prime objectives of the LMFBR alloy development program has been to develop alloys, which are swelling resistant and have the required irradiation mechanical properties for use as fuel cladding and/or use as ducts. The fuel cladding will see service in contact with flowing liquid sodium and have a surface temperature of about 4000C (-7500F) to 6500C (-12000F). A duct surrounds each bundle of fuel pins and sees service at about 3800C (-715 OF) to 55O0C ("10200F). These components will be exposed at the aforementioned elevated temperatures to neutron fluxes on the order of 1015 n/cm2s (E > 0.1 MeV), and should be capable of performing adequately to fluences on the order of 2 to 3Xl023 n/cm2 (E > 0.1 MeV). The Fe-Ni-Cr austenitic -alloys being evaluated include the austenitic stainless steels described in U.S. Patent Nos. 4,158,606; 4,407,673; and 4,421,572. In addition, Fe-Ni-Cr austenitic superalloys are being evaluated and have included those described in U.S. Patent Nos. 4,040,876; 4,129,462; 4,172,742; 4,225,364; 4,359,349; 4,359,350; 4,377,553; and U.S. Patent Application Serial No. 370,438 filed April 21, 1982. The foregoing efforts have been aimed at providing materials for the LMFBR environment. The fusion reactor, or CTR (Controlled Thermonuclear Reactor), also requires development of structural materials for use in its neutron irradiation environment. While a large number of, differing, fusion reactor designs have been proposed, a common requirement is the need for a low swelling, low activation material having good irradiation mechanical properties for use as a "first wall" material. The first wall forms a vacuum chamber which will hold the hot (up to 108 K in its interior) plasma in which the fusion reaction takes place. The plasma side of the first wall may be coated with a protective material such as graphite or silicon carbide. The opposite side of the first wall may be in contact with a fluid medium such as helium, water, liquid lithium or a liquid lithium-lead alloy, for example. Examples of some of the Fusion Reactor designs, and first wall materials being considered, are provided in J. T. Adrian Roberts, "Structural Materials in Nuclear Power Systems" (published in 1981 by Plenum Press New York) at pages 1-12, 279-319, which are hereby incorporated by reference. As in the LMFBR, the environment in which the fusion reactor first wall material will operate is an elevated temperature neutron irradiation environment. However, this fusion environment will significantly differ from the LMFBR environment in that the energy of the source neutrons from a D-T (deuterium-tritium) fusion reaction is expected to be on the order of about 14 MeV compared to the 0.1 to 1.0 MeV neutrons produced in the LMFBR fission process. This difference is important in that some of the critical alloying elements in the previously discuss austenitic alloys have (n,p) and (n,a) transmutation reactions which are activated by neutrons having energies greater than about 10 MeV, producing radioactive products with long half-lives. This leads to a nuclear waste handling and long term storage problem. A goal of the fusion reactor first wall alloy development program is to select or develop an alloy which will not only have the needed swelling resistance and mechanical properties, but will also have relatively low residual radioactivity (i.e. "low activation"), allowing relatively short burial times (e.g. 80 to 100 yrs.) prior to reprocessing of the material. To meet this low activation goal, significant restrictions on the amount of the following elements in first wall materials have been proposed: Niobium < 3-ppm; Mo < 30 ppm; Cu < 0.1 wt.%; N < 0.3 wt.%; and Ni < 0.9 wt.%. The restriction on nickel, and in most cases molybdenum, would eliminate the aforementioned austenitic Ni-Cr-Fe base alloys, developed for the LMFBR, from consideration as first wall materials. Other elements which may require significant restriction are: Ag, Bi, Tb, Ir, Eu and Bg. Since 1882, when the first austenitic manganese steel was developed by Sir Robert Hadfield, a number of additional austenitic manganese steels have been developed. For the most part, these steels have high toughness, high ductility, a high work hardening coefficient, and good abrasion resistance. Typically, these alloys have been used in commercial applications requiring high toughness and high wear resistance. Some of the nominal commercial compositions, processing, and uses of austenitic manganese steel are listed in: R. B. Ross, "Metallic Materials Specification Handbook", (1980, E. & F. N. Spon Ltd.) at pages 369, 370, 579-582; and ASM (American Society for Metals), "Metals Handbook Ninth Edition, Volume 3 - Properties and Selection: Stainless Steels, Tool Materials and Special Purpose Metals" (1980, ASM), at pages 568 to 588. The aforementioned pages from Ross and ASM are hereby incorporated by reference. An aim of the present invention is to provide alloy compositions having a combination of good neutron irradiation swelling resistance and low activation rendering the alloys suitable for use in neutron irradiation environments, such as those encountered in the LMFBR and the CTR. Accordingly, the present invention resides in an alloy having an austenitic microstructure and characterized by consisting essentially of from 20 to 40 wt.% Mn; O to 15 wt.X Cr; from 0.4 to 3.0 wt.% Si; at least one of C and N in an amount effective to stabilize said austenitic microstructure, but less than 0.7 wt.% C and less than 0.3 wt.X N; O to 0.1 wt.% P; O to 0.01 wt.% B; O to 3.0 wt.% Al; 0 to 0.5 wt.% Ni; O to 2.0 wt.% W; O to 1.0 wt.% Ti; O to 1.0 wt.% Ta; O to 2.5 wt.% V; with the remainder being essentially iron. Optionally, the alloy contains at least one of from 0.01 to 0.1 wt.% P, from 0.2 to 2.5 wt.% V, from 0.2 to 2.0 wt.% W, from 0.1 to 1.0 wt.% Ti, and from 0.1 to 1.0 wt.% Ta as a stabilizing agent. B may be added in amounts effective to enhance high temperature ductility but not more than 0.01 wt.%, and Al may be added in amounts effective to enhance liquid metal corrosion resistance and/or strength, but not more than 3 wt.% to avoid increases in activation. Preferably the Mn content of the alloy is from 25 to 40 wt.% and more preferably from 25 to 35 wt.%, with a nominal composition of about 30 wt.% being most preferred. The chromium content of the alloy is preferably from 2 to 15 wt.% and more preferably from 5 to 10 wt.%. Preferably, nitrogen is limited to less than 0.1 wt.%. Silicon is preferably present at from 0.4 to 0.8 wt.% of the alloy. The phosphorous content of the alloy is prefera- bly from 0.03 to 0.06 wit. , and more preferably from 0.03 to 0.05 wt.%. The boron content of the alloy is preferably from 0.003 to 0.006 wt.%. Preferably the strengthening agent is selected from 0.03 to 0.06 wt.% P, from 0.5 to 1.5 wt.% W, from 0.2 to 0.5 wt.% Ti, from 0.2 to 0.5 wt.% Ta, alone or in combination with each other. Preferably the following are considered as incidental impurities, with their concentrations limited to achieve a low activation alloy: Nb, Mo, Cu, N, Ni, Ag, Bi, Tb, Ir, Eu and Ba. While not wishing to be bound by theory, we believe that the understanding of, use of, and the advantageous results which may be obtained from the present invention, may be furthered by the following theory: Upon studying the compositional dependence of high-energy neutron irradiation induced swelling in Fe-Ni-Cr ternary alloys, we have shown that the compositional dependence observed resides primarily in the transient region (i.e. incubation period) of swelling and that the greatest resistance to swelling occurs in the compositional range when nickel content is from 35 to 45 wt.% and the chromium content is less than 15 wt.%. This compositional range is also characterized by anomalous property behavior where many physical properties such as thermal expansion, elastic moduli, lattice parameter and excess free energy exhibit a marked variation with composition. This anomalous behavior is best exemplified by the Invar phenomenon, wherein the thermal coefficient of expansion reaches a minimum near Fe - 35 wt.% Ni. At another composition, Fe - 7.8 wt.% Cr - 35 wt.% Ni, the thermoelastic coefficient indeed becomes zero over a significant temperature range. This composition is known as Elinvar and fortuitously corresponds almost exactly with the composition of one of the most swelling-resistant ternary alloys irradiated in the range of 400 to 6500C. This ternary alloy has the composition Fe - 7.5 wt.% Cr - 35.5 wt.% Ni. Perhaps it is only coincidental that the Invar, and particularly the Elinvar, composition correspond to the region where the duration of the transient regime of Fe-Ni-Cr austenitic alloys appears to be the longest. However, if one evaluates the current theories of void swelling1 it appears that parameters such as lattice parameters and elastic moduli indeed are important determinants of swelling behavior1 particularly when radiation-induced segregation occurs at void surfaces. Accordingly, we suggest that a direct connection may exist between the anomalous behavior compositional range and the composition range of maximum swelling resistance. We have found through review of the available literature that there exists iron-manganese base and iron-chromium-manganese base Invar-like alloys. Therefore, based on the correlation observed in the Fe-Ni and Fe-Cr-Ni systems between Invar-like properties and increased swelling resistance, it is our belief that Fe-Mn and Fe-Cr-Mn alloys having Invar behavior will also have increased swelling resistance. The Invar behavior has been observed in Fe-Mn and Fe-Mn-Cr alloys at similar iron and chromium levels and at levels of Mn comparable to those of Ni in the Fe-Ni and Fe-Ni-Cr Invar type alloys. Based on our review of the available literature we believe that the Invar phenomenon resides at Mn levels on the order of 30 weight percent. An additional advantage of the Fe-Mn and Fe-Mn-Cr alloys based on the Invar/swelling resistance correlation is a substantial reduction in residual radioactivity after fusion reactor first wall usage compared to the LMFBR Fe-Ni-Cr austenitic alloys. We further believe it to be desirable that our alloy be substantially austenitic and preferably completely austenitic. To this end, an austenite stabilizer is added. This austenite stabilizing element is selected from C and N, alone or in combination with each .other, and in an amount effective to stabilize the austenitephase, but less than 0.7 wt.% C and less than 0.3 wt.% N. The minimum amount of carbon and/or nitrogen needed for a particular alloy may be roughly estimated by referral to a Schaeffler diagram which estimates the microstructural conditions (e.g. amount of austenite, ferrite and martensite) produced by welding as a function of equivalent nickel content and equivalent chromium content. Equivalent nickel content is defined as the wt.% Ni + 0.5 x wt. Mn + 30 x wt.% C + 30 x wt.% N. Equivalent chromium content is defined as the wt.% Cr + 1.5 x wt.% Si. While the Schaeffler diagram was developed for Fe-Ni-Cr base austenitic stainless steels, we believe that it can be used to provide a rough estimate of the C+N contents required in the present-invention. More accurate assessments may be made through routine experimentation. The Schaeffler Diagram shown in A. L. Schaeffler, "Metal Progress 56," (1949) at page 680B is hereby incorporated by reference. While both carbon and nitrogen may be added in the amounts described, it is however preferred for low activation alloys that the nitrogen content be less than 0.1 wt.%. For high temperature applications such as LMFBR fuel cladding and ducts, and fusion first wall applications, the alloys according to the present invention preferably include a strengthening agent selected to provide enhanced elevated temperature tensile and creep properties. This strengthening agent may be selected from 0.01 to 0.1 wt.% P, 0.2 to 2.5 wt.% V, 0.2 to 2.0 wt.% W, and 0.1 to 1.0 wt.% Ti, and 0.1 to 1.0 wt.% Ta, alone or in combination with each other. It is believed that phosphorous will not only strengthen the alloy through phosphide precipitation, but will also act to enhance swelling resistance. However, excessive amounts of phosphorous may be deleterious from a weldability standpoint. For these reasons it is preferred that the phosphorous content be held to 0.03 to 0.06 wt.%, and more preferably 0.03 to 0.05 wt.%. Tungsten is believed to strengthen the alloy through a solid solution strengthen mechanism and metal carbide precipitation. When present, this element should be preferably held to from 0.5 to 1.5 wt.% to assure the fabricability of the alloy by conventional metal working techniques. Titanium and tantalum are very strong formers of carbide precipitates and may be used in that function here to improve ductility and creep properties as well as strength. Titanium and tantalum are preferably held to from 0.2 to 0.5 wt.%. Vanadium's preference during irradiation is being evaluated since it forms massive V(C,N) particles during thermal aging, rather than the dispersion of fine precipitates desired for good mechanical properties. Also boron may be present in the alloy at levels up to 0.01 wt.% to improve ductility. It is preferred that boron be added in conjunction with the preferred range of phosphorous (0.03 to 0.06 wt.%) to improve creep and stress rupture properties. The preferred boron range to accomplish these goals is from 0.003 to 0.006 wt.%. Aluminum may be added to the present alloys to provide improved corrosion resistance, and may be particularly necessary for applications involving contact with liquid metals, such as, lithium and lithium-lead alloys. When added, aluminum should be limited to not more than 3 wt.% to minimize handling and storage problems due to residual radioactivity. For this reason, it is preferred that the aluminum content of our alloys be from 0.5 to 2.0 wt.% where enhanced liquid metal corrosion resistance is required. Nickel may be deliberately added at levels up to 0.5 wt.%, to provide enhanced austenite stability and improved ductility. Levels above 0.5 wt.%, should be avoided in order to minimize handling and storage problems due to residual radioactivity. Most preferably nickel is not intentionally added, but is present only as an incidental impurity. Iron forms essentially the balance of these alloys. In applications having the potential of producing significant amounts of residual radioactivity, the following elements preferably, should at most be present at incidental impurity levels: Nb, Mo, Cu, N, Ni, Ag, Bi, Tb, Ir, Eu, and Ba. The tolerable levels will depend on the specific environment of use, the particular alloy composition, as well as the relevant regulations specifying the maximum level of radioactivity permitted for safe handling after a predetermined burial period. The invention will now be illustrated with reference to the following Example: EXAMPLE Alloys having the nominal melt composition aiming points shown in Table I were arc melted in a purified argon atmosphere with a non-consumable tungsten electrode. The starting materials used were basically electrolytic, high purity, virgin materials. Buttons of about 175 grams and about i" x 1" x 3" in size, were melted in water cooled copper molds. It is contemplated, that in the future the foregoing starting materials and melting technique may be replaced by higher purity starting materials, such as zone refined materials, and melting techniques allowing better control of incidental impurities. TABLE I NOMINAL ALLOY COMPOSITIONS (wit.%)* Alloy Mn Cr C N V P B Al W Ni Si Ti Ta X75 30 2 0.1 0.15 - - - - - 0.5 0.4 -- - R76 30 2 0.6 0.05 - 0.05 0.005 - - 0.5 0.4 -- - R77 30 2 0.4 0.15 1 0.05 0.005 - 1 0.5 0.4 ' -- R78 30 5 0.05 0.15 - * - - - 0.5 0.4 -- - R79 30 10 0.05 0.1 - - - - - 0.5 0.4 -- - R80 30 10 0.5 0.1 2 - 0.005 1 2 0.5 0.4 -- - R81 20 15 0.05 0.1 - - - - - 0.5 0.4 -- - R129 30 5 0.5 0.1 - 0.05 0.005 1 - - 0.4 -- - R130 30 5 0.5 0.1 - 0.05 0.005 1 - - 0.4 0.2 - R132 30 5 0.5 0.1 - 0.05 0.005 1 1 - 0.4 -- - R133 30 5 0.5 - - 0.05 0.005 - - - 0.8 -- - R134 30 5 0.5 0.1 - 0.05 0.005 1 - - 0.4 -- 0.2 *Balance essentially iron. All alloys in table I were then given a homogenization heat treatment in an inert gas for about two hours at about 12 50 OC . These alloys were then reheated in an inert gas to about 10000C and immediately thereafter given about a 50% reduction in thickness by rolling, followed by solution annealing in an inert gas at about 10306C for about h hour. Subsequently, these alloys were cold rolled for 3 to 4 additional reductions in thickness of about 40 to about 60 percent each, separated by intermediate solution anneals in an inert gas at about 10300C for about 1 hour. Each 40 to 60 percent cold reduction was typically accomplished in 2 to 4 cold rolling passes. The wrought samples of the alloys in the various metallurgical conditions shown in Table II were prepared from sheet having a thickness of about 0.25 mm. TEM (transmission electron microscopy) disks from all alloys shown in Table II and miniature tensile samples from alloy R77 were placed in the FFTF (Fast Flux Test Facility at Hanford Washington) reactor for fast neutron (0.1 < E < 1.0 MeV) irradiation exposure at about 400, 500 and 6000C. TABLE II METALLURGICAL CONDITION EMI11.1 <tb> S.A.* <SEP> I <SEP> C.W.* <SEP> S.A. <SEP> S.A. <SEP> + <SEP> C,.W. <SEP> + <SEP> A* <SEP> S.A. <SEP> + <SEP> C.W. <SEP> + <SEP> h1 <SEP> + <SEP> A2 <tb> X75, <SEP> R76-R81 <SEP> R77 <SEP> X75, <SEP> R77, <SEP> R80 <SEP> R77 <tb> *S.A. = solution annealed at 1030 C for i hour C.W. = 20 cold rolling reduction A = aging treatment at 6500C for 1 hour A1 + A2 = aging treatment at 600 C for 1 hour followed by an aging treatment at 7000C for 10 hours All heat treatments were performed in an inert atmosphere.

Claims: CLAIMS: 1. An alloy having an austenitic microstructure and characterized by consisting essentially of from 20 to 40 wt.% Mn; O to 15 wt.% Cr; from 0.4 to 3.0 wt.% Si; at least one of C and N in an amount effective to stabilize said austenitic microstructure, but less than 0.7 wt.% C and less than 0.3 wt.% N; O to 0.1 wt.% P; O to 0.01 wt.X B; O to 3.0 wt.% Al; 0 to 0.5 wt.% Ni; O to 2.0 wt.% W; O to 1.0 wt.% Ti; O to 1.0 wt.% Ta; O to 2.5 wt.% V; with the remainder being essentially iron. 2. An alloy according to claim 1, characterized in that said alloy contains from 25 to 35 wt.% Mn. 3. An alloy according to claim 1 or 2, characterized in that said alloy contains from 5 to 10 wt.% Cr. 4. An alloy according to claim 1, 2 or 3, characterized in that said alloy contains less than 0.1 wt.% N. 5. An alloy according to claim 1, 2, 3 or 4, characterized in that said alloy contains from 25 to 40 wt.% Mn. 6. An alloy according to any of claims 1 to 5, characterized in that said alloy contains from 0.03 to 0.06 wt.% P and from 0.003 to 0.006 wt.% B. 7. An alloy according to any of claims 1 to 6, characterized in that the alloy contains at least one of W, Ta and Ti in an amount of at least 0.2 wt.% as a metal carbide forming agent.

Inventors: BRAGER, HOWARD ROY, GARNER, FRANCIS ALBERT
Applicants: WESTINGHOUSE ELECTRIC CORPORATION
Application year: 1985
Main classification: C22C38
IPC codes: C22C38, G21B1, G21C3