Enrique J. Lavernia

A High-Performance Corrosion-Resistant Iron-Based Amorphous Metal - The Effects of Composition, Structure and Environment on Corrosion Resistance

New corrosion-resistant, iron-based amorphous metals have been identified from published data or developed through combinatorial synthesis, and tested to determine their relative thermal phase stability, microstructure, mechanical properties, damage tolerance, and corrosion resistance. Some alloy additions are known to promote glass formation and to lower the critical cooling rate [F. Guo, S. J. Poon, Applied Physics Letters, 83 (13) 2575-2577, 2003]. Other elements are known to enhance the corrosion resistance of conventional stainless steels and nickel-based alloys [A. I. Asphahani, Materials Performance, Vol. 19, No. 12, pp. 33-43, 1980] and have been found to provide similar benefits to iron-based amorphous metals. Many of these materials can be cast as relatively thick ingots, or applied as coatings with advanced thermal spray technology. A wide variety of thermal spray processes have been developed by industry, and can be used to apply these new materials as coatings. Any of these can be used for the deposition of the formulations discussed here, with varying degrees of residual porosity and crystalline structure. Thick protective coatings have now been made that are fully dense and completely amorphous in the as-sprayed condition. An overview of the High-Performance Corrosion Resistant Materials (HPCRM) Project will be given, with particular emphasis on the corrosion resistance of several different types of iron-based amorphous metals in various environments of interest. The salt fog test has been used to compare the performance of various wrought alloys, melt-spun ribbons, arc-melted drop-cast ingots, and thermal-spray coatings for their susceptibility to corrosion in marine environments. Electrochemical tests have also been performed in seawater. Spontaneous breakdown of the passive film and localized corrosion require that the open-circuit corrosion potential exceed the critical potential. The resistance to localized corrosion is seawater has been quantified through measurement of the open-circuit corrosion potential (E{sub corr}), the breakdown potential (E{sub crit}) and the repassivation potential (E{sub rp}). The greater the difference between the open-circuit corrosion potential and the repassivation potential ({Delta}E), the more resistant a material is to modes of localized corrosion such as pitting and crevice corrosion. Cyclic polarization (CP) was used as a means of measuring the critical potential (E{sub crit}) relative to the open-circuit corrosion potential (E{sub corr}). Linear polarization (LP) has been used to determine the corrosion current (i{sub corr}) and the corresponding corrosion rate. Other aspects of the materials will also be discussed, as well as potential applications.

FY05 HPCRM Annual Report: High-Performance Corrosion-Resistant Iron-Based Amorphous Metal Coatings

New corrosion-resistant, iron-based amorphous metals have been identified from published data or developed through combinatorial synthesis, and tested to determine their relative corrosion resistance. Many of these materials 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 some very aggressive environments, including concentrated calcium-chloride brines at elevated temperature. Two Fe-based amorphous metal formulations have been found that appear to have corrosion resistance comparable to, or better than that of Ni-based Alloy C-22, based on breakdown potential and corrosion rate. Both Cr and Mo provide corrosion resistance, B enables glass formation, and Y lowers critical cooling rate (CCR). SAM1651 has yttrium added, and has a nominal critical cooling rate of only 80 Kelvin per second, while SAM2X7 (similar to SAM2X5) has no yttrium, and a relatively high critical cooling rate of 610 Kelvin per second. Both amorphous metal formulations have strengths and weaknesses. SAM1651 (yttrium added) has a low critical cooling rate (CCR), which enables it to be rendered as a completely amorphous thermal spray coating. Unfortunately, it is relatively difficult to atomize, with powders being irregular in shape. This causes the powder to be difficult to pneumatically convey during thermal spray deposition. Gas atomized SAM1651 powder has required cryogenic milling to eliminate irregularities that make flow difficult. SAM2X5 (no yttrium) has a high critical cooling rate, which has caused problems associated with devitrification. SAM2X5 can be gas atomized to produce spherical powders of SAM2X5, 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. Comparable metallic alloys such as SAM2X5 and SAM1651 may also experience crevice corrosion under sufficiently harsh conditions. Accelerated crevice corrosion tests are now being conducted to intentionally induce crevice corrosion, and to determine those environmental conditions where such localized attack occurs. Such materials are extremely hard, and provide enhanced resistance to abrasion and gouges (stress risers) from backfill operations, and possibly even tunnel boring. 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. These new materials provide a viable coating option for repository engineers. SAM2X5 and SAM1651 coatings can be applied with thermal spray processes without any significant loss of corrosion resistance. Both Alloy C-22 and Type 316L stainless lose their resistance to corrosion during thermal spraying. Containers for the transportation, storage and disposal of spent nuclear fuel (SNF) and high-level radioactive waste (HLW) with corrosion resistant coatings are envisioned. For example, an enhanced multi-purpose container (MPC) could be made with such coatings, leveraging existing experience in the fabrication of such containers. These coating materials could be used to protect the final closure weld on SNF/HLW disposal containers, eliminate need for stress mitigation. Integral drip shield could be produced by directly spraying it onto the disposal container, thereby eliminating the need for an expensive titanium drip shield. In specific areas where crevice corrosion is anticipated, such as the contact point between the disposal container and pallet, HVOF coatings could be used to buildup thickness, thereby selectively adding corrosion life where it is needed. Both SAM2X5 & SAM1651 have high boron content which enable them to absorb neutrons and therefore be used for criticality control in baskets. Alloy C-22 and 316L have no neutron absorber, and cannot be used for such functions. Borated stainless steel and G