Synthesis and Performance of Fe-based Amorphous Alloys for Nuclear Waste Applications

Recent developments in multi-component Fe-based amorphous alloys have shown that these novel materials exhibit outstanding corrosion resistance compared to typical crystalline alloys such as high-performance stainless steels and Ni-based C-22 alloy. During the past decade, amorphous alloy synthesis has advanced to allow for the casting of bulk metallic glasses. In several Fe-based alloy systems it is possible to produce glasses with cooling rates as low as 100 K/s. At such low cooling rates, there is an opportunity to produce amorphous solids through industrial processes such as thermal spray-formed coatings. Moreover, since cooling rates in typical thermal spray processing exceed 1000 K/s, novel alloy compositions can be synthesized to maximize corrosion resistance (i.e. adding Cr and Mo) and to improve radiation compatibility (adding B) and still maintain glass forming ability. The applicability of Fe-based amorphous coatings in typical environments where corrosion resistance and thermal stability are critical issues has been examined in terms of amorphous phase stability and glass-forming ability through a coordinated computational analysis and experimental validation. For example, a wedge casting technique has been applied to examine bulk glass forming alloys by combining multiple thermal probes with a measurement based kinetics analysis and a computational thermodynamics evaluation to elucidate the phase selection competition and critical cooling rate conditions. Based upon direct measurements and kinetics modeling it is evident that a critical cooling rate range should be considered to account for nucleation behavior and that the relative heat flow characteristics as well as nucleation kinetics are important in judging ease of glass formation. Similarly, a novel computational thermodynamics approach has been developed to explore the compositional sensitivity of glass-forming ability and thermal stability. Also, the synthesis and characterization of alloys with increased cross-section for thermal neutron capture will be outlined to demonstrate that through careful design of alloy composition it is possible to tailor the material properties of the thermally spray-formed amorphous coating to accommodate the challenges anticipated in typical nuclear waste storage applications over tens of thousands of years in a variety of corrosive environments

SYNTHESIS AND PERFORMANCE OF FE-BASED AMORPHOUS ALLOYS FOR NUCLEAR WASTE REPOSITORY APPLICATIONS

In several Fe-based alloy systems it is possible to produce glasses with cooling rates as low as 100 K/s that exhibit outstanding corrosion resistance compared to typical crystalline alloys such as high-performance stainless steels and Ni-based C-22 alloy. Moreover, novel alloy compositions can be synthesized to maximize corrosion resistance (i.e. adding Cr and Mo) and to improve radiation compatibility (adding B) and still maintain glass forming ability. The applicability of Fe-based amorphous coatings in typical environments where corrosion resistance and thermal stability are critical issues has been examined in terms of amorphous phase stability and glass-forming ability through a coordinated computational analysis and experimental validation. Similarly, a novel computational thermodynamics approach has been developed to explore the compositional sensitivity of glass-forming ability and thermal stability. Also, the synthesis and characterization of alloys with increased cross-section for thermal neutron capture will be outlined to demonstrate that through careful design of alloy composition it is possible to tailor the material properties of the thermally spray-formed amorphous coating to accommodate the challenges anticipated in typical nuclear waste storage applications over tens of thousands of years in a variety of corrosive environments

DOE-DARPA High-Performance Corrosion-Resistant Materials (HPCRM), Annual HPCRM Team Meeting & Technical Review

The overall goal is to develop high-performance corrosion-resistant iron-based amorphous-metal coatings for prolonged trouble-free use in very aggressive environments: seawater & hot geothermal brines. The specific technical objectives are: (1) Synthesize Fe-based amorphous-metal coating with corrosion resistance comparable/superior to Ni-based Alloy C-22; (2) Establish processing parameter windows for applying and controlling coating attributes (porosity, density, bonding); (3) Assess possible cost savings through substitution of Fe-based material for more expensive Ni-based Alloy C-22; (4) Demonstrate practical fabrication processes; (5) Produce quality materials and data with complete traceability for nuclear applications; and (6) Develop, validate and calibrate computational models to enable life prediction and process design

Electrochemical Studies of Passive Film Stability on Fe48Mo14Cr15Y2C15B Amorphous Metal in Seawater at 90oC and 5M CaCl2 at 105oC

Several Fe-based amorphous metal formulations have been identified that appear to have corrosion resistance comparable to, or better than that of Ni-based Alloy C-22 (UNS N06022), based on measurements of breakdown potential and corrosion rate in seawater. Both chromium (Cr) and molybdenum (Mo) provide corrosion resistance, boron (B) enables glass formation, and rare earths such as yttrium (Y) lower critical cooling rate (CCR). Amorphous Fe{sub 48.0}Cr{sub 15.0}Mo{sub 14.0}B{sub 6.0}C{sub 15.0}Y{sub 2.0} (SAM1651) has a low critical cooling rate (CCR) of less than 80 Kelvin per second, due to the addition of yttrium. The low CCR enables it to be rendered as a completely amorphous material in practical materials processes. While the yttrium enables a low CCR to be achieved, it makes the material relatively difficult to atomize, due to increases in melt viscosity. Consequently, the powders produced thus far have had irregular shape, which had made pneumatic conveyance during thermal spray deposition difficult

Electrochemical Studies of Passive Film Stability on Fe48Mo14Cr15Y2C15B Amorphous Metal in Seawater at 90oC and 5M CaCl2 at 105oC

Several Fe-based amorphous metal formulations have been identified that appear to have corrosion resistance comparable to, or better than that of Ni-based Alloy C-22 (UNS N06022), based on measurements of breakdown potential and corrosion rate in seawater. Both chromium (Cr) and molybdenum (Mo) provide corrosion resistance, boron (B) enables glass formation, and rare earths such as yttrium (Y) lower critical cooling rate (CCR). Amorphous Fe{sub 48.0}Cr{sub 15.0}Mo{sub 14.0}B{sub 6.0}C{sub 15.0}Y{sub 2.0} (SAM1651) has a low critical cooling rate (CCR) of less than 80 Kelvin per second, due to the addition of yttrium. The low CCR enables it to be rendered as a completely amorphous material in practical materials processes. While the yttrium enables a low CCR to be achieved, it makes the material relatively difficult to atomize, due to increases in melt viscosity. Consequently, the powders produced thus far have had irregular shape, which had made pneumatic conveyance during thermal spray deposition difficult

Corrosion Resistances of Iron-Based Amorphous Metals with Yttrium and Tungsten Additions in Hot Calcium Chloride Brine & Natural Seawater: Fe48Mo14CR15Y2C15B6 and Variants

The passive film stability of several Fe-based amorphous metal formulations have been found to be comparable to that of stainless steels and Ni-based Alloy C-22 (UNS No. N06022), based on electrochemical measurements of the passive film breakdown potential and general corrosion rates. Electrochemical studies of the passive film stability of SAM1651 are reported here. Chromium (Cr), molybdenum (Mo) and tungsten (W) provide corrosion resistance; boron (B) enables glass formation; and rare earths such as yttrium (Y) lower critical cooling rate (CCR). Yttrium-containing SAM1651, also known as SAM7 (Fe{sub 48.0}Cr{sub 15.0}Mo{sub 14.0}B{sub 6.0}C{sub 15.0}Y{sub 2.0}), has a critical cooling rate (CCR) of approximately 80 Kelvin per second, while yttrium-free SAM2X5 (Fe{sub 49.7}Cr{sub 17.7}Mn{sub 1.9}Mo{sub 7.4}W{sub 1.6}B{sub 15.2}C{sub 3.8}Si{sub 2.4}) has a higher critical cooling rate of approximately 600 Kelvin per second. SAM1651's low CCR enables it to be rendered as a completely amorphous material in practical materials processes. While the yttrium enables a low CCR to be achieved, it makes the material relatively difficult to atomize, due to increases in melt viscosity. Consequently, the powders have irregular shape, which makes pneumatic conveyance during thermal spray deposition difficult. The reference material, nickel-based Alloy C-22, is an outstanding corrosion-resistant engineering material. Even so, crevice corrosion has been observed with C-22 in hot sodium chloride environments without buffer or inhibitor. SAM1651 may also experience crevice corrosion under sufficiently harsh conditions. Both Alloy C-22 and Type 316L stainless lose their resistance to corrosion during thermal spraying, due to the formation of deleterious intermetallic phases which depletes the matrix of key alloy elements, whereas SAM1651 can be applied as coatings with the same corrosion resistance as a fully-dense completely amorphous melt-spun ribbon, provided that its amorphous nature is preserved during thermal spraying. Materials synthesis and characterization is discussed. Data showing the corrosion resistance of SAM1651 in hot concentrated calcium chloride, as well as natural seawater are presented, and compared to a number of reference materials

High-Performance Corrosion-Resistant Iron-Based Amorphous Metals - The Effects of Composition, Structure and Environment: Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4

Several Fe-based amorphous metal formulations have been identified that appear to have corrosion resistance comparable to (or better than) that of Ni-based Alloy C-22 (UNS No. N06022), based on measurements of breakdown potential and corrosion rate in seawater. Both chromium (Cr) and molybdenum (Mo) provide corrosion resistance, boron (B) enables glass formation, and rare earths such as yttrium (Y) lower critical cooling rate (CCR). SAM2X5 (Fe{sub 49.7}Cr{sub 17.7}Mn{sub 1.9}Mo{sub 7.4}W{sub 1.6}B{sub 15.2}C{sub 3.8}Si{sub 2.4}) has no yttrium, and is characterized by relatively high critical cooling rates of approximately 600 Kelvin per second. Data for the SAM2X5 formulation is reported here. In contrast to yttrium-containing iron-based amorphous metals, SAM2X5 can be readily gas atomized to produce spherical powders which enable more facile thermal spray deposition. The reference material, nickel-based Alloy C-22, is an outstanding corrosion-resistant engineering material. Even so, crevice corrosion has been observed with C-22 in hot sodium chloride environments without buffer or inhibitor. SAM2X5 also experiences crevice corrosion under sufficiently harsh conditions. Both Alloy C-22 and Type 316L stainless lose their resistance to corrosion during thermal spraying, due to the formation of deleterious intermetallic phases which depletes the matrix of key alloy elements, whereas SAM2X5 can be applied as coatings with the same corrosion resistance as a fully-dense completely amorphous melt-spun ribbon, provided that its amorphous nature is preserved during thermal spraying. The hardness of Type 316L Stainless Steel is approximately 150 VHN, that of Alloy C-22 is approximately 250 VHN, and that of HVOF SAM2X5 ranges from 1100-1300 VHN [MRS12-13]. Such hardness makes these materials particularly attractive for applications where corrosion-erosion and wear are also issues. Since SAM2X5 has high boron content, it can absorb neutrons efficiently, and may therefore find useful applications as a criticality control material within the nuclear industry

Electrochemical Studies of Passive Film Stability on Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4 Amorphous Metal in Seawater at 90oCElectrochemical Studies of Passive Film Stability on Fe49.7Cr17.7Mn1.9Mo7.4W1.6B15.2C3.8Si2.4 Amorphous Metal in Seawater at 9

An iron-based amorphous metal, Fe{sub 49.7}Cr{sub 17.7}Mn{sub 1.9}Mo{sub 7.4}W{sub 1.6}B{sub 15.2}C{sub 3.8}Si{sub 2.4} (SAM2X5), with very good corrosion resistance was developed. This material was prepared as a melt-spun ribbon, as well as gas atomized powder and a thermal-spray coating. During electrochemical testing in several environments, including seawater at 90 C, the passive film stability was found to be comparable to that of high-performance nickel-based alloys, and superior to that of stainless steels, based on electrochemical measurements of the passive film breakdown potential and general corrosion rates. This material also performed very well in standard salt fog tests. Chromium (Cr), molybdenum (Mo) and tungsten (W) provided corrosion resistance, and boron (B) enabled glass formation. The high boron content of this particular amorphous metal made it an effective neutron absorber, and suitable for criticality control applications. This material and its parent alloy maintained corrosion resistance up to the glass transition temperature, and remained in the amorphous state during exposure to relatively high neutron doses

High-Performance Corrosion-Resistant Materials: Iron-Based Amorphous-Metal Thermal-Spray Coatings: SAM HPCRM Program ? FY04 Annual Report ? Rev. 0 - DARPA DSO & DOE OCRWM Co-Sponsored Advanced Materials Program

The multi-institutional High Performance Corrosion Resistant Materials (HPCRM) Team is cosponsored by the Defense Advanced Projects Agency (DARPA) Defense Science Office (DSO) and the Department of Energy (DOE) Office of Civilian Radioactive Waste Management (OCRWM), and has developed new corrosion-resistant, iron-based amorphous metals that can be applied as coatings with advanced thermal spray technology. Two compositions have corrosion resistance superior to wrought nickel-based Alloy C-22 (UNS No. N06022) in very aggressive environments, including concentrated calcium-chloride brines at elevated temperature. Corrosion costs the Department of Defense billions of dollars every year, with an immense quantity of material in various structures undergoing corrosion. For example, in addition to fluid and seawater piping, ballast tanks, and propulsions systems, approximately 345 million square feet of structure aboard naval ships and crafts require costly corrosion control measures. The use of advanced corrosion-resistant materials to prevent the continuous degradation of this massive surface area would be extremely beneficial. The Fe-based corrosion-resistant, amorphous-metal coatings under development may prove of importance for applications on ships. Such coatings could be used as an 'integral drip shield' on spent fuel containers, as well as protective coatings that could be applied over welds, thereby preventing exposure to environments that might cause stress corrosion cracking. In the future, such new high-performance iron-based materials could be substituted for more-expensive nickel-based alloys, thereby enabling a reduction in the $58-billion life cycle cost for the long-term storage of the Nation's spent nuclear fuel by tens of percent

Penetration of molten silicon into a bed of fines

During the casting process of silicon the mould must be buffered from the high temperatures of the molten silicon to prevent the mould melting and this is typically done by the operators laying down a layer of crushed silicon particles (fines) prior to pouring of the molten silicon. It is useful for operators to know how deep they should make the layer the fines so as to adequately separate the molten silicon from the mould. In this paper, we consider a model for the penetration of molten silicon into the pre-laid layer of silicon fines, which provides a predictive tool for estimating the necessary depth of fines in order to prevent the molten silicon touching the mould. The mathematical model developed here considers the flow of molten silicon as a Darcy flow and solidification due to heat flow as a one-phase Stefan problem. We are able to find a numerical solutions to this model, and from this we are able to extract data regarding the penetration depth of the molten silicon into the fines before solidification occurs. Our model and numerical solution can been seen as a first step toward understanding this important part of the casting process for silicon