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At least 19 records

Corrosion-Resistant Plug Materials for Geothermal Well Fluid Control

Conventional cements and plugs are challenged by corrosion in CO 2 -rich and extreme geothermal environments, due to the hostile chemistry and high temperatures. Thermite-based sealing and well intervention technologies are being applied in the oil and gas industry, combining the energy delivery capability of thermite materials with the sealing characteristics of low melt temperature alloys. The thermite reaction products (ceramics) and the sealing alloys used in these plugs both have very attractive corrosion properties, and their operating envelopes extend into geothermal conditions. Thermite plugs and platforms, without supplemental sealing materials, have been considered for nuclear waste isolation, carbon sequestration, and geothermal applications due to the geochemical stability of the ceramic product and its very high service temperature. This study addresses corrosion resistance of the thermite reaction products. A range of engineered thermite systems which yield thermite reaction products including pure aluminum oxide, feldspar, or aluminosilicate solid solutions (in addition to the iron produced in thermite reactions) was developed. These materials were evaluated for their strong acid resistance (pH 1), carbonate resistance (sodium carbonate) and thermal shock resistance (600 °C heating → cold water quenching repeated three times). Performance of different materials was evaluated based on the changes in mechanical properties, water-fillable porosity, phase changes under stress conditions. The aluminosilicate product exhibited very good corrosion resistance, both from material loss and strength perspectives, while the other products performed with varying degrees of stability. This paper presents the results of the thermite corrosion studies and describes the novel tools being deployed, and under development, to satisfy challenging barrier and intervention applications.

02 PETROLEUM↗

Non-Magnetic, Tough, Corrosion- and Wear-Resistant Knives From Bulk Metallic Glasses and Composites

Quality knives are typically fabricated from high-strength steel alloys. Depending on the application, there are different requirements for mechanical and physical properties that cause problems for steel alloys. For example, diver's knives are generally used in salt water, which causes rust in steel knives. Titanium diver's knives are a popular alternative due to their salt water corrosion resistance, but are too soft to maintain a sharp cutting edge. Steel knives are also magnetic, which is undesirable for military applications where the knives are used as a tactical tool for diffusing magnetic mines. Steel is also significantly denser than titanium (8 g/cu cm vs. 4.5 g/cu cm), which results in heavier knives for the same size. Steel is hard and wear-resistant, compared with titanium, and can keep a sharp edge during service. A major drawback of both steel and titanium knives is that they must be ground or machined into the final knife shape from a billet. Since most knives have a mirrored surface and a complex shape, manufacturing them is complex. It would be more desirable if the knife could be cast into a net or near-net shape in a single step. The solution to the deficiencies of titanium, steel, and ceramic knives is to fabricate them using bulk metallic glasses (or composites). These alloys can be cast into net or near-net shaped knives with a combination of properties that exceed both titanium and steel. A commercially viable BMG (bulk metallic glass) or composite knife is one that exhibits one or all of the following properties: It is based on titanium, has a self-sharpening edge, can retain an edge during service, is hard, is non-magnetic, is corrosion-resistant against a variety of corrosive environments, is tough (to allow for prying), can be cast into a net-shape with a mirror finish and a complex shape, has excellent wear resistance, and is low-density. These properties can be achieved in BMG and composites through alloy chemistry and processing. For each desired property for knife fabrication and performance, there is an alloy development strategy that optimizes behavior. Although BMG knives have been demonstrated as far back as 1995, they never found commercial success because they had to be ground (which presented problems because the alloys contained beryllium), they weren't low cost (because they weren't cast to a net-shape), they were brittle (because they were made with a low-quality commercial material), and they had extremely poor corrosion resistance (because corrosion was not well-understood in these materials). Ultimately, these shortcomings prevented the widespread commercialization. In the current work, the inventors have applied more than a decade of research on BMGs from Caltech and JPL to develop a better understanding of how to make BMG knives that exhibit an optimal combination of properties, processing and cost. Alloys have been developed based in titanium (and other metals), that exhibit high toughness, high hardness, excellent corrosion resistance, no ferromagnetism, edge-retaining selfsharpening, and the ability to be cast like a plastic using commercially available casting techniques (currently used by commercial companies such as Liquidmetal Technologies and Visser Precision Casting). The inventors argue that depending on the application (diving, military, tactical, utility, etc.) there is an optimal combination of design and alloy composition. Moreover, with new casting technologies not available at the inception of these materials, net-shaped knives can be cast into complex shapes that require no aftermarket forming, except for sharpening using water-cooled polishing wheel. These combinations of discoveries seek to make low-cost BMG knives commercially viable products that have no equal among metal or ceramic knives. Current work at JPL focuses on net-shape casting of these alloys and testing their mechanical properties versus commercially available knives to demonstrate their benefits.

Hoffman, Douglas C.↗

Progress in Understanding the Origins of Excellent Corrosion Resistance in Metallic Alloys: From Binary Polycrystalline Alloys to Metallic Glasses and High Entropy Alloys

Some of the factors responsible for good corrosion resistance of select polycrystalline and emerging alloys in chloride solutions are discussed with a goal of providing some perspectives on the current status and future directions. Traditional metallic glass alloys, single phase high entropy alloys (HEAs), early metallic glasses, and high entropy metallic glasses are all emerging corrosion-resistant alloys (CRAs) that utilize traditional strategies for improved corrosion resistance as well as take advantage of some other novel beneficial attributes. These materials enjoy many degrees of freedom as far as choice of both composition and structure, providing great flexibility in the pursuit of superior corrosion resistance. The new materials depart from classical solvent-solute type polycrystalline binary or ternary alloys. Thus, such emerging materials provide significant opportunities to achieve even greater improvements in corrosion resistance in harsh environments. Several examples of the unique corrosion properties of selected materials in the context of modern theories of corrosion are discussed herein. Discussion is restricted to solid-solution binary or ternary polycrystalline alloys, several metallic glass alloys, and single phase HEAs. A common feature of many CRAs is that composition and microstructure often affect both passivity and resistance to localized corrosion that can be divided into initiation, stabilization, and propagation stages. Enormous complexities in protective oxide structures and chemistries and the large number of combinatorial possibilities in newer materials such as HEAs preclude trial-and-error approaches and perhaps even combinatorial experimental design. Computational materials methodologies will be required in the search for new corrosion-resistant alloys in these material classes. The search must consider the best scientific insights available regarding how major and minor alloy additions, as well as various microstructural attributes, contribute to corrosion mitigation. Additional scientific insights, as they emerge, will enable choices beyond the reliance on high concentrations of alloying elements that are known to affect passivity breakdown and pit stabilization. A challenge is to connect the “basic attributes” of an alloy with its properties. The strength of this connection will likely require new scientific principles enabling deep multiphysics insights in order to link feature(s) such as composition and metallurgical phases to the desired corrosion properties. Application of data informatics will likely also play a role given the plethora of variables that are important in corrosion and the difficulty in assessing all relationships. Here, the opportunity exists to accelerate the design of emerging materials for high corrosion resistance.

36 MATERIALS SCIENCE↗

Material Selection and Corrosion Studies of Candidate Bearing Materials for Use in Molten Chloride Salt

Molten chloride salts are being given strong consideration for use in heat transfer and storage in concentrating solar power (CSP) systems as well as in some nuclear reactor applications. Containment of the molten salt, particularly at the highest temperatures, is a major material concern and has received considerable study. Another material issue is the pumps that will be required to move the molten salt along with the bearing materials that will be required to have sufficient corrosion resistance as well as wear resistance in the high temperature salt. A pair of coordinated studies in our laboratory has addressed the corrosion, and the wear issues of candidate bearing materials including the selection of candidate materials as well as their performance in a molten sodium chloride-potassium chloride-magnesium chloride salt environment. This work addresses the selection of candidate materials and their chemical compatibility with the molten salt. The studies have identified material pairs that have suitable properties for use as bearings that would be immersed in molten chloride salt.

14 SOLAR ENERGY↗

Electrochemical Impedance Spectroscopy of Alloys in a Simulated Space Shuttle Launch Environment

Corrosion studies began at NASA/Kennedy Space Center in 1966 during the Gemini/Apollo Programs with the evaluation of long-term protective coatings for the atmospheric protection of carbon steel. An outdoor exposure facility on the beach near the launch pad was established for this purpose at that time. The site has provided over 35 years of technical information on the evaluation of the long-term corrosion performance of many materials and coatings as well as on maintenance procedures. Results from these evaluations have helped NASA find new materials and processes that increase the safety and reliability of our flight hardware, launch structures, and ground support equipment. The launch environment at the Kennedy Space Center (KSC) is extremely corrosive due to the combination of ocean salt spray, heat, humidity, and sunlight. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pad were rendered even more severe by the acidic exhaust from the solid rocket boosters. Over the years, many materials have been evaluated for their corrosion performance under conditions similar to those found at the launch pads. These studies have typically included atmospheric exposure and evaluation with conventional electrochemical methods such as open circuit potential (OCP) measurements, polarization techniques, and electrochemical impedance spectroscopy (EIS). The atmosphere at the Space Shuttle launch site is aggressive to most metals and causes severe pitting in many of the common stainless steel alloys such as type 304L stainless steel (304L SS). A study was undertaken to find a more corrosion resistant material to replace the existing 304L SS tubing. This paper presents the results from atmospheric exposure as well as electrochemical measurements on the corrosion resistance of AL-6XN (UNS N08367) and 254-SMO (UNS S32154). Type 304L SS (UNS S30403) was used as a control. Conditions at the Space Shuttle launch pad were simulated by using a hydrochloric acid (HC1) and alumina (Al203) slurry rinse for the atmospheric exposure and an electrolyte consisting of 3.55% sodium chloride (NaC1) with increased concentrations of hydrochloric acid (HC1) for the electrochemical measurements. The results from both types of measurements revealed the superior corrosion performance of the higher-alloyed materials. Unlike 304L SS, 254-SMO and AL-6XN exhibited a significantly improved resistance to corrosion as the concentration of hydrochloric acid in he 3.55% NaCl electrolyte solution was increased.

Calle, L. M.↗

Anodization Compatibility of Eutectic Aluminum–Cerium Alloys

Anodizing is the most common method for producing corrosion resistant layer coatings for aluminum alloys. It is possible to use anodizing with most commercial aluminum alloys to increase material corrosion resistance, but often the brittle, passive oxide layer formed during anodization does not adhere well to the material, reducing effectiveness, and overall compatibility. Therefore, it is important for the compatibility and effect of anodization to be studied for any newly developed alloys. Recently developed eutectic Al–Ce alloys offer advantages like high castability, limited or no heat treatment requirements, and high-temperature strength retention. In this work, Al–Ce alloys are shown to have good compatibility with current processes and may exhibit improved adhesion of passivated layer because intermetallic phases anchor the anodized product to unconverted bulk. The source of these phenomena and their effect on material corrosion and layer adhesion properties of Al–Ce alloys will be discussed and compared with results from common commercial aluminum alloys.

Sims, Zachary↗

High Tensile Strength Amalgams for In-Space Fabrication and Repair

Amalgams are well known for their use in dental practice as a tooth filling material. They have a number of useful attributes that include room temperature fabrication, corrosion resistance, dimensional stability, and very good compressive strength. These properties well serve dental needs but, unfortunately, amalgams have extremely poor tensile strength, a feature that severely limits other potential applications. Improved material properties (strength and temperature) of amalgams may have application to the freeform fabrication of repairs or parts that might be necessary during an extended space mission. Advantages would include, but are not limited to: the ability to produce complex parts, a minimum number of processing steps, minimum crew interaction, high yield - minimum wasted material, reduced gravity compatibility, minimum final finishing, safety, and minimum power consumption. The work presented here shows how the properties of amalgams can be improved by changing particle geometries in conjunction with novel engineering metals.

Grugel, Richard N.↗

Materials Research for High Speed Civil Transport and Generic Hypersonics-Metals Durability

This report covers a portion of an ongoing investigation of the durability of titanium alloys for the High Speed Civil Transport (HSCT). Candidate alloys need to possess an acceptable combination of properties including strength and toughness as well as fatigue and corrosion resistance when subjected to the HSCT operational environment. These materials must also be capable of being processed into required product forms while maintaining their properties. Processing operations being considered for this airplane include forming, welding, adhesive bonding, and superplastic forming with or without diffusion bonding. This program was designed to develop the material properties database required to lower the risk of using advanced titanium alloys on the HSCT.

Schulz, Paul↗

Long term compatibility of nitrogen tetroxide with metals - Results at the ten-year milestone

Analyses and results are reported of a test program to establish the effects of long-term (10 years or more) contact of materials with nitrogen textroxide MON-1 for the purpose of designing chemical propulsion system components which can be used for current as well as future planetary spacecraft. The test materials included aluminum alloy, corrosion-resistant steel, titanium alloy, and nickel. The weight and appearance of each specimen were observed, including the presence of deposits, etching, pitting, and cracking. Aluminum alloy and steel were rated satisfactory with minor reservations, titanium alloy was satisfactory, and nickel was unsatisfactory. Criteria for ratings are shown.

Moran, C. M.↗

Long term compatability of hydrazine with metals: Results at the ten-year milestone

A test program to establish the effects of long term contact of materials with hydrazine for the purpose of designing chemical propulsion system components which can be used for current as well as future planetary spacecraft was analyzed. Materials included the following: aluminum alloys, corrosion resistant steels, and a titanium alloy. Material ratings relative to the 10 year milepost are assigned. The propellant was found to be stable. With minor exceptions, the materials tested were rated acceptable for a 10 year mission.

Moran, C. M.↗

Process Optimization of Bismaleimide (BMI) Resin Infused Carbon Fiber Composite

Engineers today are presented with the opportunity to design and build the next generation of space vehicles out of the lightest, strongest, and most durable materials available. Composites offer excellent structural characteristics and outstanding reliability in many forms that will be utilized in future aerospace applications including the Commercial Crew and Cargo Program and the Orion space capsule. NASA's Composites for Exploration (CoEx) project researches the various methods of manufacturing composite materials of different fiber characteristics while using proven infusion methods of different resin compositions. Development and testing on these different material combinations will provide engineers the opportunity to produce optimal material compounds for multidisciplinary applications. Through the CoEx project, engineers pursue the opportunity to research and develop repair patch procedures for damaged spacecraft. Working in conjunction with Raptor Resins Inc., NASA engineers are utilizing high flow liquid infusion molding practices to manufacture high-temperature composite parts comprised of intermediate modulus 7 (IM7) carbon fiber material. IM7 is a continuous, high-tensile strength composite with outstanding structural qualities such as high shear strength, tensile strength and modulus as well as excellent corrosion, creep, and fatigue resistance. IM7 carbon fiber, combined with existing thermoset and thermoplastic resin systems, can provide improvements in material strength reinforcement and deformation-resistant properties for high-temperature applications. Void analysis of the different layups of the IM7 material discovered the largest total void composition within the [ +45 , 90 , 90 , -45 ] composite panel. Tensile and compressional testing proved the highest mechanical strength was found in the [0 4] layup. This paper further investigates the infusion procedure of a low-cost/high-performance BMI resin into an IM7 carbon fiber material and the optical, chemical, and mechanical analyses performed.

Ehrlich, Joshua W.↗

High-resolution characterization of ceramic-metal interface of TiN coating on ferritic-steels for nuclear application

Advanced fuel cladding is critical for fast reactors, offering sufficient thermal conductivity, mechanical and dimensional stability and radiation tolerance of the cladding base material. Additionally, it must provide corrosion resistance and high temperature coolant compatibility on the cladding outer surface, as well as chemical stability on the cladding inner wall against fuel cladding chemical interaction (FCCI). TiN ceramic coating has been considered an effective diffusion barrier for inner and outer cladding-walls for enhanced performance. The TiN-metal interface microstructure and chemistry play a critical role in coating bond strength and integrity under harsh conditions. High-resolution transmission electron microscopy characterization of ceramic-metal interface at atomic resolution in unirradiated, irradiated and thermal cycled conditions were performed. The interface remained intact after irradiation up to 200 dpa or thermal cycling five times up to 550 °C. In conclusion, this work discusses the potential impact of these results on coating performance and design for advanced claddings.

36 - MATERIALS SCIENCE↗

Effect of grain refinement on high temperature steam oxidation of an FeCrAl alloy

FeCrAl alloys are promising candidates to replace Zr alloys as fuel cladding materials in nuclear light-water reactors. Grain refinement has been indicated to improve irradiation resistance. To enhance corrosion resistance as well, the effects of grain refinement on steam corrosion behavior were investigated in this work. Samples of Kanthal D alloy (Fe-21Cr-5Al) with two different grain sizes (coarse-grained and ultrafine-grained) were exposed to steam at 1200 °C for 2 hrs. In conclusion, results indicate improved steam corrosion resistance in ultrafine-grained Kanthal D with formation of a thinner protective Al oxide layer and the presence of a thin underlying Cr oxide layer.

36 MATERIALS SCIENCE↗

Development of Corrosion Resistant Coatings for Structural Materials for Liquid Fueled Molten Salts Reactors Applications (Final Report)

Current structural alloys, code certified for the MSRs temperature ranges, contain high levels of chromium, making them highly susceptible to molten halide salt corrosion. One potential solution to circumvent the need for code certification of novel alloys, which is expensive and time consuming, is to design claddings that will protect the underlying code certified materials from corrosion damage during operation. In this work, we examined the corrosion of Ni and Cu electroplated, Ni and CuNi weld overlay, Mo-laser clad, and carburized claddings on SS316H for use in molten salt reactor environments. After characterization of the cladded materials (Task 1), static corrosion tests were used to assess corrosion resistance of the claddings in typical molten fluoride salts (Task 2). The corrosion tests were performed in molten FLiNaK at 700°C up to 1000 hours. Pre- and post-corrosion Scanning Electron Microscopy (SEM), energy-dispersive-spectroscopy (EDS), Transmission Electron Microscopy (TEM), X-ray Diffraction (XRD) and glow-discharge-optical-emission-spectroscopy (GDOES) were performed on cladding cross-sections and surfaces to evaluate degradation. The Cu and Ni electroplated samples, as well as the carburized samples, showed excellent corrosion resistance relative to the bare SS316H. To assess high temperature cladding stability, ageing experiments were performed at temperatures up to 900 C in inert atmosphere for the electroplated and carburized samples and a diffusion model was developed to predict long term cladding behavior (Task 3). It was found that the Cu cladding was basically insensitive to the high temperature ageing, except for small secondary phases forming at the interface. On the other hand, the Ni electroplated cladding experienced significant interdiffusion. Nevertheless, the gain in corrosion resistance for a 100μm Ni electroplated cladding is phenomenal, with more than 50% reduction in chromium dissolution from the substrate material for the first 15 years of salt exposure at 700°C. To assess radiation resistance and phase stability, high-temperature 4MeV Ni heavy ion irradiation was performed across the cladding/substrate interface up to 50 displacement-per-atom (DPA) at 500°C and 700°C to assess the phase stability and irradiation behaviors of the electroplated systems (Task 4). The Ni and Cu electroplated systems did not experience void swelling at the contrary to the SS316H substrate due to their nanocrystalline nature. Some level of recrystallization was observed in the cladding, as well as radiation induced segregation and enhanced diffusion. The interface acted as a potent sink for point defects with the presence of a void denuded zone. The mechanical properties of the claddings were assessed using thermal shock, micro-indentation, nano-indentation, and four-point bend testing experiments (Task 5). These experiments were performed on the claddings in as-received, corroded, irradiated, and thermally aged states to determine the effects of typical molten salt reactor environments on cladding integrity. No significant mass loss was observed after repeated thermal shocks. While the electroplated samples softened after high-temperature ageing, irradiation hardening compensate this effect, such that there is little different with the as-received materials. The results of these experiments suggest that the electroplated (copper/nickel) show the greatest promise for application in molten salt reactor development. These claddings prevented any chromium dissolution from occurring during the static corrosion experiments. Additionally, they demonstrated favorable properties for high temperature diffusion, phase stability, interfacial mechanical properties, and irradiation resistance. Weld-overlay cladding are also of great interest and could reach properties similar to the electroplated samples upon optimization (especially with multiple weld passes). The carburized SS316H showed excellent behavior as well, but more work needs to be done to assess their long-term stability. Finally, the Mo-laser clad system was not pursued further due to the manufacturing challenges. It is also worth noting that the Ni cladding systems should behave relatively well in terms of weldability since the Ni-weld overlay microstructure and associated corrosion rate are sound. While the NiCu weld-overlay has even lower corrosion rates than the Ni-weld overlay, more studies on welding of Cu-electroplated systems are necessary since Cu clusters are known to embrittle steels.

36 MATERIALS SCIENCE↗

High Tensile Strength Amalgams for In-Space Repair and Fabrication

Amalgams are defined as an alloy of mercury with one or more other metals. These, along with those based on gallium (also liquid at near room temperature), are widely used in dental practice as a tooth filling material. Amalgams have a number of useful attributes that indude room temperature compounding. corrosion resistance, dimensional stability, and good compressive strength. These properties well serve dental needs but, unfortunately, amalgams have extremely poor tensile strength, a feature that severely limits their applications. The work presented here demonstrates how, by modifying particle geometry, the tensile strength of amalgams can be increased and thus extending the range of potential applications. This is relevant to, for example, the freeform fabrication of replacement parts that might be necessary during an extended space mission. Advantages, i.e. Figures-of-Merit. include the ability to produce complex parts, minimum crew interaction, high yield - minimum wasted material, reduced gravity compatibility, minimum final finishing, safety, and minimum power consumption.

Grugel, R. N.↗

Status of Understanding for Bearing Materials

The structural materials and potential failure modes for high technology aircraft gas turbine bearings are reviewed. Among the failure modes discussed for iron-base through-hardened bearing materials are fatigue, surface distress, and corrosion. It is shown that the sub-surface initiated rolling-contact fatigue failure mode is reasonably well understood and in most cases can be controlled by proper material selection and design. Current bearing materials provide long life and high reliability in existing applications. A new generation of materials are being developed which will provide improved fracture toughness, better corrosion resistance, and a further extension of bearing fatigue life. Bearing problems due to surface distress, caused by a variety of surface and near surface anomalies, are less well understood. This area will require the implementation of an interdisciplinary effort to improve the level of understanding of metallic surface-lubricant reactions and interactions.

E N Bamberger↗

Carbon aerogels with integrated engineered macroporous architectures for improved mass transport

Carbon aerogels (CAs) combine unique properties including ultra-high surface area, high electrical conductivity, corrosion resistance, and robust mechanical properties making them ideal materials for electrochemical applications. Traditional CA synthesis results in isotropic, random nanoporous networks that work well for applications relying on diffusional mass transport. However, many applications would benefit from integration of engineered macroporous network structures that enable directed pressure-gradient-driven mass transport. In this study, we report on using 3D-printed sacrificial polymeric templates to generate templated CAs (t-CAs) with integrated engineered nonrandom macroporous network structures. Specifically, we used projection micro-stereo-lithography (PμSL) and two-photon polymerization direct laser writing (2PP-DLW) to fabricate millimeter-to-centimeter-sized 3D sacrificial polymeric templates with features ranging from tens of microns (PμSL) to 100s of nanometers (2PP-DLW). T-CAs were fabricated by infiltrating the templates with resorcinol-formaldehyde (RF) precursor solution, followed by carbonization at 1050 °C to simultaneously convert the RF gel to a CA and decompose the 3D-printed template, leaving an embedded templated macroporous network structure behind. X-ray computer tomography confirms integration of the macroporous architecture defined by the template. The templated macroporous architecture improves mass transport in t-CAs compared to traditional bulk CA as demonstrated by more uniform activation and their response in electrochemical cyclic voltammetry and galvanostatic charge-discharge tests.

36 MATERIALS SCIENCE↗

High-Temperature Thermophysical Property Measurement of Proposed Gen3 CSP Containment Materials

Abstract The US Department of Energy (DOE) has sponsored an initiative to improve the thermal efficiency of Concentrating Solar Power (CSP) systems. To approach parity with conventional fossil fuel-based electricity generation, the operating temperature of the CSP power cycle must exceed 700°C with integrated thermal energy storage. The materials used to house this high-temperature heat transfer media must be thermally stable and corrosion resistant. However, the temperature-dependent thermophysical properties of commonly used containment materials (nickel alloys and alumina-based firebricks) are either not well known or poorly understood. In this report, the high-temperature thermal properties of thirteen (13) candidate containment materials proposed by the CSP community are tested using laser flash analysis and differential scanning calorimetry.

Brankovic, Sonja A.↗