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Nickel-Based Superalloy Resists Embrittlement by Hydrogen

A nickel-based superalloy that resists embrittlement by hydrogen more strongly than does nickel alloy 718 has been developed. Nickel alloy 718 is the most widely used superalloy. It has excellent strength and resistance to corrosion as well as acceptably high ductility, and is recognized as the best alloy for many high-temperature applications. However, nickel alloy 718 is susceptible to embrittlement by hydrogen and to delayed failure and reduced tensile properties in gaseous hydrogen. The greater resistance of the present nickel-based superalloy to adverse effects of hydrogen makes this alloy a superior alternative to nickel alloy 718 for applications that involve production, transfer, and storage of hydrogen, thereby potentially contributing to the commercial viability of hydrogen as a clean-burning fuel. The table shows the composition of the present improved nickel-based superalloy in comparison with that of nickel alloy 718. This composition was chosen to obtain high resistance to embrittlement by hydrogen while maintaining high strength and exceptional resistance to oxidation and corrosion. The most novel property of this alloy is that it resists embrittlement by hydrogen while retaining tensile strength greater than 175 kpsi (greater than 1.2 GPa). This alloy exhibits a tensile elongation of more than 20 percent in hydrogen at a pressure of 5 kpsi (approximately equal to 34 MPa) without loss of ductility. This amount of elongation corresponds to 50 percent more ductility than that exhibited by nickel alloy 718 under the same test conditions.

Lee, Jonathan↗

Hydrothermal corrosion of 2nd generation FeCrAl alloys for accident tolerant fuel cladding

As part of an effort to develop advanced fuel cladding for use in light water reactors, several FeCrAl alloys have been developed at Oak Ridge National Laboratory. A second generation of these alloys bearing additional alloying elements over the previously tested model alloys were tested in boiling water reactor (BWR) conditions to determine their resistance to hydrothermal corrosion. Coupons with alloy compositions Fe–10Cr–6Al–2Mo, Fe–13Cr–5Al–2Mo, Fe–13Cr–6Al–2Mo, Fe–13Cr–7Al–2Mo, and Fe–13Cr–5Al–2Mo–1Nb were tested in normal water chemistry (NWC) and hydrogen water chemistry (HWC) for 9 months in continuously refreshing autoclaves. Commercial FeCrAl alloy APMT and Zircaloy-2 were also tested for comparison. Among samples exposed to HWC, Fe–13Cr–7Al–2Mo performed worst with an average mass loss of 1.3 mg/cm2 over 9 months. This mass loss represents an estimated thickness loss of approximately 60 μm over 6 years. Samples exposed to NWC had very small mass losses of less than 0.15 mg/cm2 or mass gains up to 0.05 mg/cm2. Based on the results of this testing, the 2nd generation FeCrAl alloys tested exhibit low wall thickness loss and are suitable in terms of corrosion resistance for use as LWR cladding in BWR-HWC and BWR-NWC under normal operating conditions.

Raiman, Stephen↗

Silicon nitride: A ceramic material with outstanding resistance to thermal shock and corrosion

The known physical, mechanical and chemical properties of reaction-sintered silicon nitride are summarized. This material deserves interest especially because of its unusually good resistance to thermal shock and corrosion at high temperatures. Two types are distinguished: reaction-sintered (porous) and hot-pressed (dense) Si3N4. Only the reaction-sintered material which is being produced today in large scale as crucibles, pipes, nozzles and tiles is considered.

Huebner, K. H.↗

Additive manufacturing and testing of a ceramic heat exchanger for high-temperature and high-pressure applications for concentrating solar power

Heat exchangers with excellent corrosion and oxidation resistances are essential for the next-generation concentrating solar power (CSP) plants using a molten salt heat transfer fluid and a supercritical CO 2 Brayton power cycle that can operate at temperatures > 700 °C for higher efficiencies. Techniques were developed for additively manufacturing ceramic materials for applications involving high temperature, high pressure, and high corrosion resistance as needed for the CSP application. Based on a previous ceramic heat exchanger design with its cross-section geometry of the flow channels optimized for heat transfer and mechanical strength, lab-scale prototype heat exchangers, with integrated headers and incorporated flow channel dimensional compensations, were fabricated by using the binder jetting process. The printed prototype heat exchangers were successfully densified through the processes of liquid polymer infiltration and pyrolysis. In addition, thermophysical properties of the densified silicon carbide parts were measured to provide necessary design information. Experimental heat transfer testing of the lab-scale prototype heat exchanger was conducted, and the experimental data agreed reasonably well with the simulated results. Furthermore, this agreement provides validation of the simulation models for their applicability to the development of a full-scale ceramic heat exchanger.

14 SOLAR ENERGY↗

Crack Growth Rate and Fracture Toughness Tests on Irradiated Ex-Plant Materials

The performance of structural materials is critical for the safe and economic operation of light water reactors. Exposed to neutron irradiation during service, the reactor core internal materials can undergo significant microstructural and microchemical changes, leading to irradiation hardening and embrittlement. To ensure the structural integrity and functionality of nuclear reactor components during long-term operation, material degradation and damage mechanisms must be understood and managed adequately. In this work, irradiated materials harvested from the decommissioned Zorita reactor were studied for their cracking susceptibility and fracture resistance as a function of irradiation dose up to 47 displacement per atom (dpa). The material is a Type 304 stainless steel sectioned from the baffle plates of this pressurized water reactor with 38 years of service. Crack growth rate and fracture toughness J-resistance (J-R) curve tests were performed in low-corrosion-potential environments at ~315°C. All samples behaved similarly under cyclic loading, and no deteriorated corrosion-fatigue behavior was observed in the test environments. Under constant stress intensity factors, most samples did not show elevated crack growth rates, suggesting an adequate stress corrosion cracking resistance in the test environments. However, an unstable cracking behavior was observed in a 47-dpa sample, resulting in significantly higher crack growth rates than expected at high stress intensity factors. Crack instability was also observed in a 0.06-dpa sample but did not lead to a sustained high crack growth rate. The impact of neutron irradiation was more evident in the fracture toughness J-R curve tests. As the dose increased, the J-R curve declined considerably and became very shallow at high doses. A fully intergranular fracture morphology was also observed among the high-dose samples ruptured in an air atmosphere at room temperature. This brittle fracture mode in the absence of high temperature water environment confirmed a high degree of embrittlement of this material resulting from its service exposure to neutron irradiation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Time exposure studies on stress corrosion cracking of aluminum 2014-T6, 2219-T87, 2014-T651, 7075-T651, and titanium 6Al-4V

The effect of a constant applied stress in crack initiation of aluminum 2014-T6, 2219-T87, 2014-T651, 7075-T651 and titanium 6Al-4V has been investigated. Aluminum c-ring specimens (1-inch diameter) and u-band titanium samples were exposed continuously to a 3.5% NaCl solution (pH 7) and organic fluids of ethyl, methyl, and iso-propyl alcohol (reagent purity), and demineralized distilled water. Corrosive action was observed to begin during the first and second day of constant exposure as evidenced by accumulation of hydrogen bubbles on the surface of stressed aluminum samples. However, titanium stressed specimens showed no reactions to its environment. Results of this investigation seems to suggest that aluminum 2014-T6, aluminum 7075-T651 and aluminum 2014-T651 are susceptible to stress corrosion cracking in chloride solution (NaCl), while aluminum 2219-T87 seem to resist stress corrosion cracking in sodium chloride at three levels of stress (25%, 50%, and 75% Y.S.). In organic fluids of methyl, ethyl, and iso-propyl alcohol, 2014-T6 and 7075-T651 did not fail by SCC; but 2014-T651 was susceptible to SCC in methly alcohol, but resistant in ethyl alcohol, iso-propyl alcohol and demineralized distilled water.

Terrell, J.↗

Time exposure studies on stress corrosion cracking of aluminum 2014-T6, aluminum 7075-T651, and titanium 6Al-4V

The effect of a constant applied stress in crack initiation of aluminum 2014-T6, 7075-T651 and titanium 6A1-4V has been investigated. Aluminum c-ring specimens (1-inch diameter) and u-band titanium samples were exposed continuously to a 3.5% NaCl solution (pH 6) and organic fluids of ethyl, methyl, and iso-propyl alcohol (reagent purity). Corrosive action was observed to begin during the first and second day of constant exposure as evidenced by accumulation of hydrogen bubbles on the surface of stressed aluminum samples. However, a similar observation was not noted for titanium stressed specimens. Results of this investigation seems to suggest that aluminum 2014-T6, aluminum 7075-T651 are susceptible to stress corrosion cracking in chloride solution (NaCl); while they (both alloys) seem to resist stress corrosion cracking in methyl alcohol, ethyl alcohol, iso-propyl alcohol, and demineralized distilled water. Titanium 6A1-4V showed some evidence of susceptibility to SCC in methanol, while no such susceptibility was exhibited in ethanol, iso-propyl alcohol and demineralized distilled water.

Terrell, J.↗

Fabrication of Lightweight Radiation Shielding Composite Materials by Field Assisted Sintering Technique (FAST)

Advances in radiation shielding technologies are needed to protect humans and electronic components from all threats of space radiation over long durations. In this paper, we report on the use of the innovative and novel fabrication technology known as Field Assisted Sintering Technology (FAST) to fabricate lightweight material with enhanced radiation shielding strength to safeguard humans and electronics suitable for next generation space exploration missions. The base materials we investigated were aluminum (Al), the current standard material for space hardware, and Ultra-High Molecular Weight Polyethylene (UHMWPE), which has high hydrogen content and resistance to nuclear reaction from neutrons, making it a good shielding material for both gamma radiation and particles. UHMWPE also has high resistance to corrosive chemicals, extremely low moisture sensitivity, very low coefficient of friction, and high resistance to abrasion. We reinforced the base materials by adding high density (ie, high atomic weight) metallic material into the composite. These filler materials included: boron carbide (B4C), tungsten (W), tungsten carbide (WC) and gadolinium (Gd).

Prasad, Narasimha↗

Corrosion of Zinc Cold Spray Coatings in a Wet Sweet and Sour Gas Environment

Internal corrosion is a problem for steel pipelines transporting natural gas or CO 2 containing water and partial pressures of H 2 S higher than 0.3 kPa (0.05 psi). This work aims to mitigate internal corrosion in steel pipelines transporting natural gas containing H 2 S using cold spray coatings. Two types of the cold spray binary metallic coatings (zinc chromium [ZnCr]. zinc niobium [ZnNb]) were studied using electrochemical techniques: potentiodynamic polarization, linear polarization resistance, and electrochemical impedance spectroscopy. The corrosion resistance of cold spray coatings (ZnCr, ZnNb) was evaluated in an environment containing 4 bar CO 2 pressure, simulating the partial pressures found in gas transmission lines over a solution of 3.5 wt% NaCl heated to 40°C. A concentration of 0.003 M Na 2 S 2 O 3 ·5H 2 O, corresponding to H 2 S partial pressures around 0.079 bar (1.146 psi), was used to simulate sour conditions. Postcorrosion surface characterization was performed using a scanning electron microscope (SEM) equipped with an energy-dispersive x-ray spectroscope (EDS) and x-ray diffraction analysis. The data showed that the presence of 0.003 M Na 2 S 2 O 3 ·5H 2 O shifted the corrosion potential to more anodic values and decreased the corrosion current density. Both coatings showed similar behavior after 1 h of exposure in the CO 2 /H 2 S environment, indicating that similar electrochemical reactions were occurring on ZnNb and ZnCr. SEM images and EDS surface analyses for specimens showed a significant change in the surface chemical composition of carbon steel coated with ZnNb and ZnCr after 24 h of immersion. In the presence of thiosulfate (under sour conditions), the formation of corrosion product layers (ZnCO 3 and ZnS) on top of ZnNb and ZnCr coatings increased their corrosion resistance, which helped to reduce their corrosion by a factor of 2. Under a sweet environment, the corrosion rates for steel coated with cold spray coatings after 14 d of exposure are lower than that for galvanized steel by a factor of 5 due to the ZnCO 3 layer formed on top of the coatings. The ZnCO 3 layer formed on the steel surface acts as a physical barrier against corrosion by blocking the diffusion of corrosive species to the surface. No localized attack was observed. ZnCr Cold spray coating with defect showed promising corrosion protection against CO 2 corrosion (sweet corrosion) after 14 d of exposure to a CO 2 environment. Here, the scratch on the coating simulated damage created in service, and it was deep enough to expose the substrate material (steel). The formation of zinc oxide (ZnO) and zinc carbonate (ZnCO 3 ) on the scratch confirmed the cathodic protection of the steel by ZnCr and ZnNb coatings.

36 MATERIALS SCIENCE↗

Synthetic sea water - An improved stress corrosion test medium for aluminum alloys

A major problem in evaluating the stress corrosion cracking resistance of aluminum alloys by alternate immersion in 3.5 percent salt (NaCl) water is excessive pitting corrosion. Several methods were examined to eliminate this problem and to find an improved accelerated test medium. These included the addition of chromate inhibitors, surface treatment of specimens, and immersion in synthetic sea water. The results indicate that alternate immersion in synthetic sea water is a very promising stress corrosion test medium. Neither chromate inhibitors nor surface treatment (anodize and alodine) of the aluminum specimens improved the performance of alternate immersion in 3.5 percent salt water sufficiently to be classified as an effective stress corrosion test method.

Humphries, T. S.↗

Development of the technology for the fabrication of reliable laminar flow control panels

Various configurations of porous, perforated and slotted materials were flow tested to determine if they would meet the LFC surface smoothness and flow requirements. The candidate materials were then tested for susceptibility to clogging and for resistance to corrosion. Of the materials tested, perforated titanium, porous polyimide, and slotted assemblies demonstrated a much greater resistance to clogging than other porous materials.

Weiss, D. D.↗

Oxidation-resistance Mechanism and Other Properties of Molybdenum Disilicide

The outstanding oxidation resistance of molybdenum disilicide at 2400 F and above was found to depend on the formation of a protective siliceous coating which a-cristobalie has been identified. Molybdenum disilicide is not inherently resistant to oxidation and in powdered form burns at low temperatures.Melting and casting experiments have demonstrated the decomposition of the material at the melting point. The room-temperature modulus of elasticity has been determined and electric-resistivity data are given to 2000 F.

MATERIALS, PROPERTIES-CORROSION RESISTANCE↗

Corrosion evaluation of Al-Cu-Mn-Zr cast alloys in 3.5% NaCl solution

Corrosion behavior of cast Al-Cu-Mn-Zr (ACMZ) and RR350 alloys was compared to a cast 319 alloy in 3.5 wt.% NaCl. After 168 h immersion, ACMZ and RR350 alloys suffered from preferential attack adjacent to intermetallic particles decorated at grain boundaries while the attack in 319 occurred in eutectic Al-Si dendritic boundaries. Electrochemical data allowed semiquantitative comparison of alloy resistance to corrosion initiation, and ACMZ type alloys, including RR350 and three alloys with higher Cu, were considered more resistant than 319 due to the absence of deleterious Si particles. In case of 319, such Si particles presumably drove higher micro-galvanic influence to initiate and sustain Al corrosion. With lower susceptibility to corrosion initiation, ACMZ alloys should exhibit higher or at minimum similar resistance compared to cast 319.

36 MATERIALS SCIENCE↗

Environmental protection to 922K (1200 F) for titanium alloys

Evaluations are presented of potential coating systems for protection of titanium alloys from hot-salt stress-corrosion up to temperatures of 755 K (900 F) and from oxidation embrittlement up to temperature of 922 K (1200 F). Diffusion type coatings containing Si, Al, Cr, Ni or Fe as single coating elements or in various combinations were evaluated for oxidation protection, hot-salt stress-corrosion (HSSC) resistance, effects on tensile properties, fatigue properties, erosion resistance and ballistic impact resistance on an alpha and beta phase titanium alloy (Ti-6Al-2Sn-4Zr-2Mo). All of the coatings investigated demonstrated excellent oxidation protectiveness, but none of the coatings provided protection from hot-salt stress-corrosion. Experimental results indicated that both the aluminide and silicide types of coatings actually decreased the HSSC resistance of the substrate alloy. The types of coatings which have typically been used for oxidation protection of refractory metals and nickel base superalloys are not suitable for titanium alloys because they increase the susceptibility to hot-salt stress-corrosion, and that entirely new coating concepts must be developed for titanium alloy protection in advanced turbine engines.

Groves, M. T.↗

The Corrosion of Magnesium and of the Magnesium Aluminum Alloys Containing Manganese

The extensive use of magnesium and its alloys in aircraft has been seriously handicapped by the uncertainties surrounding their resistance to corrosion. This problem has been given intense study by the American Magnesium Corporation and at the request of the Subcommittee on Materials for Aircraft of the National Advisory Committee for Aeronautics this report was prepared on the corrosion of magnesium. The tentative conclusions drawn from the experimental facts of this investigation are as follows: the overvoltage of pure magnesium is quite high. On immersion in salt water the metal corrodes with the liberation of hydrogen until the film of corrosion product lowers the potential to a critical value. When the potential reaches this value it no longer exceeds the theoretical hydrogen potential plus the overvoltage of the metal. Rapid corrosion consequently ceases. When aluminum is added, especially when in large amounts, the overvoltage is decreased and hydrogen plates out at a much lower potential than with pure magnesium. The addition of small amount of manganese raises the overvoltage back to practically that of pure metal, and the film is again negative.

Boyer, J A↗