Beryllium fluoride coating as a corrosion retardant for beryllium.
High temperature modified Be fluoride, rhombic tridymite, protects Be against aqueous corrosion
Odonnell, P. M.↗
SEARCH · Engineering Papers
Results for “Corrosion Protection”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
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A Low-Cost Iron-Based Current Collector for Alkaline Battery Electrodes
The use of three-dimensional porous nickel foam as the current collector of the nickel hydroxide electrode adds significantly to the cost of the nickel-based alkaline rechargeable batteries. Although iron is considerably less expensive than nickel, iron corrodes at the operating potential of the nickel hydroxide electrode. We have found that a 70–100 nm thick thermal coating of cobalt ferrite spinel protects the iron from corrosion. Such a coated iron substrate was found to be stable against corrosion even when polarized anodically at 10 mA cm -2 in 30% potassium hydroxide electrolyte for 1000 h. While the thermal coating of cobalt ferrite protected iron against corrosion, incorporation of lithium ions into the coating was found to enhance the electrical conductivity of the coating. XPS and EXAFS studies confirmed that the enhanced conductivity resulted from an increase in the population of Co 3+ in the ferrite spinel lattice. An inexpensive iron (steel) substrate protected by such a coating when used as a nickel hydroxide battery electrode exhibited a specific capacity of 0.25 Ah g -1 at C/5 discharge rate, comparable to a nickel hydroxide electrode based on a relatively expensive nickel foam substrate. The steel-based electrode also exhibited no noticeable degradation over 150 cycles at C/2 rate. This demonstration of a robust and economical steel substrate presents a unique opportunity for reducing the cost of the nickel hydroxide battery electrode in alkaline batteries
25 ENERGY STORAGE↗
Combined Experimental and Modeling Study of the Interactions of Acid Gas with Common Spacecraft Surfaces for Fire Safety Applications
A fire in a spacecraft poses detrimental consequences and risks mission success in addition to crew safety. This is compounded during long-duration missions when the crew has limited options to recover from a fire. A common spacecraft fire concern is the smoldering of wire insulation, typically made from Polyvinyl chloride (PVC) or Polytetrafluoroethylene (PTFE). This creates acid gases such as Hydrogen Chloride (HCl), Hydrogen Fluoride (HF) and Hydrogen Cyanide (HCN). These poisonous gases are hazardous to the crew. They also interact with common surfaces within the spacecraft more than dominant combustion products such as CO2 and H2O. This makes them more difficult to track for potential fire detection techniques, or for postfire clean-up. It is imperative to be able to understand and predict the fate of these poisonous species in a microgravity environment in order to design a safe vehicle. HCl interacts with a number of materials inside a spacecraft. Primary among these materials is aluminum, which is abundantly used due to its strong and light weight nature. Aluminum has a natural oxide layer that protects it from corrosion but is typically treated to enhance this oxide layer. Among these treatments is a chromate conversion coating (CCC), which provides a thin enough protective oxide layer to still conduct electricity, and a traditional anodized material that has a thicker oxide layer that does not conduct electricity. Nomex is another common material found inside a spacecraft. It is a flame-resistant woven polymer that is related to nylon. This commercially available material is used for cargo storage bags and as a fire barrier. Physics-based models were developed to predict the uptake of HCl by these materials. The ultimate objective of these models is to predict the fate of HCl within the spacecraft so that sensors can be placed in meaningful locations in future missions based on the model predictions. To support these modeling efforts, experiments were performed in a cast acrylic test cell that measured the difference between the inlet and outlet concentration of HCl after inserting a sample rod of the test material. Different uptake capacities were realized for each type of sample tested. A computational fluid dynamics model (CFD) model of the reactor was then constructed that used a one-step global reaction rate with calibratable reaction (or kinetic) constants. These constants were calibrated to match the HCl uptake on the CCC aluminum samples, and the same kinetic constants were then tested for the stock and anodized aluminum samples. Model predictions matched the experimental data for the stock aluminum, and to a much lesser extent, the anodized aluminum. The model was additionally validated at different flow rates, sample surface areas, and inlet concentrations, and showed good agreement for all stock and CCC samples. The model did not accurately predict the HCl uptake in the anodized samples compared to the other two types of aluminum. Adjusting the kinetic constants and transport properties did little to improve the prediction. X-Ray Photoelectron Spectroscopy (XPS) was used to determine that the oxide layer thickness of anodized aluminum is approximately 5,000 nm, compared to 250 nm for CCC and 50 nm for stock. XPS also revealed presence of chlorine further down in the aluminum oxide layer in anodized samples than CCC and stock samples after the samples were saturated with HCl, indicating that accounting for diffusion of HCl into the oxide layer is important for accurate prediction of HCl uptake onto anodized aluminum. Consequently, a multi-scale model was developed and tested. First, a single pore inside the anodized aluminum oxide layer was modeled and is referred to as the pore-scale model. In this model, HCl diffused through the pore and reacted with the aluminum oxide pore wall to create aluminum chloride. The sample was then saturated when the mass transfer resistance through the growing aluminum chloride layer became too large for the HCl to reach the aluminum oxide wall and continue the reaction. This pore-scale model was coupled to the reactor-scale model using a concentration-dependent diffusion coefficient, resulting in much more accurate predictions (approximately half the sum square error of the aforementioned reactor-scale model that produced good agreement for stock and CCC) for a variety of operating conditions. The amount of water vapor or relative humidity (RH) in the flow during a reactor experiment was determined to influence HCl uptake. Experiments were performed to understand the interaction of gaseous HCl with aluminum surfaces in the presence of water vapor. The results show that increasing levels of RH increased the capacity of aluminum to adsorb HCl but decreased the capacity of Nomex to uptake HCl. A series of tests were performed on individual aluminum samples after they had been saturated with a fixed concentration of HCl in dry air conditions with the goal of determining how their HCl uptake capacity changes after various treatments with water relative to the original saturation tests. HCl-saturated aluminum samples subjected to a second dry air flow at the same HCl concentration as the original test had an uptake of 23.5% of the original sample with no treatment in between. Saturated aluminum samples subjected to an air flow with a RH of 90% in between tests had an uptake of 35.6% of the original. Saturated aluminum samples submerged in distilled water for 12 hours in between tests had an uptake of 82.2% of the original sample. Previously saturated aluminum tested with HCl and a 50% RH air flow resulted in similar uptake characteristics in multiple repeated tests. The experiments show the profound effect water vapor has on HCl uptake onto aluminum surfaces. In the samples subjected to water vapor or liquid water, capillary condensation and capillary diffusion alters the transport of HCl significantly. A model was proposed that developed a relationship between RH and the coefficient of HCl diffusion in aluminum chloride. This produced an “S-shaped” curve with diffusion coefficient as a function of RH, with 45% RH represented as the point where the diffusion coefficient is halfway between no water saturation and 100% water saturation in the aluminum chloride product layer. No difference in uptake characteristics for the experiment or model were realized between 50% and 62% RH. The results from the large-scale microgravity experiment, Saffire, are discussed as they pertain to the fate of HCl throughout a spacecraft. HCl was released, both as a standalone event, and in concurrence with the burning of a structured cloth. These events only produced a small response in the far field HCl sensor, while a PMMA burn that did not produce HCl had a significantly greater response. A ground-based large-scale facility was constructed to flow acid gas at the scale and configuration realized in the Saffire experiments. A CFD model of this duct was constructed to test kinetic parameters developed in this work at a larger scale and different geometric configuration and to predict the results of the large-scale facility. The models developed in this work were used to interpret the results of the microgravity tests and lead the discussion on what further experiments and models are needed in order to predict the fate of acid gas in a spacecraft environment. To summarize, the major contributions of this work are as follows: the capacity to uptake HCl, with and without the presence of water vapor, was measured for a variety of real spacecraft surfaces. Several different models (single reactor-scale, multiscale, spacecraft-scale) were developed and with the aid of modeling, the rate of uptake for those surfaces was also predicted and validated. The kinetic parameters determined from the small-scale reactor experiments and models were used to predict large-scale and microgravity tests. Conclusions from this research will be used in the design of spacecraft vehicles and large-scale microgravity fire safety experiments. The models built by this work will aid designers in sensor placement and could be used to predict acid gas transport from fires in partial gravity, as would be seen in Lunar and Martian habitats.
fire safety↗
Current status of environmental barrier coatings for Si-Based ceramics
Silicon-based ceramics are the leading candidates for high temperature structural components in next generation gas turbine engines. One key drawback of silicon-based ceramics for such an application is volatilization of the protective silica scale in water vapor and the resulting rapid ceramic recession. Therefore, the realization of Si-based ceramics components in advanced gas turbine engines depends on the development of protection schemes from water vapor attack. Currently, plasma-sprayed external environmental barrier coatings (EBCs) arc the most promising approach. In the late 1980s and early 1990s a wide range of refractory oxide materials were tested as coatings on Si-based ceramics to provide protection from hot corrosion. After the discovery of silica volatilization in water vapor in the early 1990s, the focus of EBC development research has been shifted towards the protection from water vapor attack. Experience learned form the earlier coating developmental effort provided the foundation upon which more complex and advanced EBC coatings have been developed. This paper will discuss the brief history and the current status of EBC development for Si-based ceramics with the main focus on water vapor protection.
Lee, K. N.↗
Corrosion fatigue of 2219-T87 aluminum alloy
Corrosion fatigue studies were conducted on bare, chemical conversion coated, and anodized 2219-T87 aluminum alloy. These tests were performed using a rotating beam machine running at a velocity of 2500 rpm. The corrosive environments tested were distilled water, 100 ppm NaCl, and 3.5 percent NaCl. Results were compared to the endurance limit in air. An evaluation of the effect of protective coatings on corrosion fatigue was made by comparing the fatigue properties of specimens with coatings to those without.
Mcmillan, V. C.↗
Liquid Galvanic Coatings for Protection of Imbedded Metals
Coating compositions and methods of their use are described herein for the reduction of corrosion in imbedded metal structures. The coatings are applied as liquids to an external surface of a substrate in which the metal structures are imbedded. The coatings are subsequently allowed to dry. The liquid applied coatings provide galvanic protection to the imbedded metal structures. Continued protection can be maintained with periodic reapplication of the coating compositions, as necessary, to maintain electrical continuity. Because the coatings may be applied using methods similar to standard paints, and because the coatings are applied to external surfaces of the substrates in which the metal structures are imbedded, the corresponding corrosion protection may be easily maintained. The coating compositions are particularly useful in the protection of metal-reinforced concrete.
MacDowell, Louis G.↗
The kinetics of the PuO 2 to Pu 2 O 3 conversion
Here in an oxidizing environment, the oxide formed on plutonium (Pu) metal is composed of a plutonium dioxide (PuO 2 ) top layer and a thin cubic plutonium sesquioxide (Pu 2 O 3 ) middle layer. In a reducing environment, the PuO 2 layer auto-reduces to cubic Pu 2 O 3 . The speed and extent of this conversion depend on the combination of temperature and time. While PuO 2 provides a strong diffusion barrier against unwanted Pu corrosion by gaseous species (like hydrogen), Pu 2 O 3 does not, since its crystal structure has chains of oxygen vacancies. The kinetics of the PuO 2 reduction are, therefore, of fundamental interest and enable researchers to better protect Pu from corrosion. In this report, the oxygen-diffusion-limited kinetics of the dioxide to sesquioxide conversion were obtained by dynamically heating a PuO 2 -covered Pu sample from 294 to 418 K in a high-vacuum vessel equipped with an in situ spectroscopic ellipsometer. The physical/chemical constraints in the conversion process were combined with the ellipsometry method of multi-sample analysis to track the percentage of PuO 2 and to compute the extent of Pu 2 O 3 formation. The resulting diffusion coefficients were compared against and then combined with complementary literature data to produce a comprehensive set of kinetic parameters for reliably modeling oxide conversion over a larger temperature range than spanned by prior studies. The extracted thermal activation energy barrier (43.7 kJ/mol) and pre-exponential factor (5.0 × 10 -10 cm 2 /s) for the oxygen-diffusion-limited process can be used to accurately model the PuO 2 to Pu 2 O 3 transformation in vacuum and/or inert gas applications.
36 MATERIALS SCIENCE↗
OXYGEN EVOLUTION FROM THE MMO ANODE CATHODIC PROTECTION SYSTEM AND ITS EFFECT ON THE CORROSION OF THE SOIL-SIDE BOTTOM PLATE OF AN ABOVE GROUND STORAGE TANK
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SHUKLA, PAVAN K↗
Electrochemical study of the dissolution of oxide films grown on type 316L stainless steel in molten fluoride salt
The corrosion behavior of oxide films grown on Type 316L stainless steel (SS) in molten FLiNaK (LiF-NaF-KF: 46.5−11.5−42 mol.%) salt was investigated. The results show that the oxide film formed on Type 316L SS is unstable and can only temporarily protect materials from corrosion in molten FLiNaK salt. Based on the electrochemical impedance spectroscopy, the oxide dissolution rate is calculated to be 0.85 nm/h at 700 °C in molten FLiNaK salt. Finally, after the oxide film dissolved, Cr and Fe are selective dealloyed from the steel, leading to intergranular corrosion of Type 316L SS in molten fluoride salt.
EIS↗
Novel Chalcopyrites for Advanced Photoelectrochemical Water Splitting
With the support of DoE’s EERE office, our team has established a unique tool-chest of capabilities, including theoretical modeling (Lawrence Livermore National Laboratory: LLNL), state-of-the-art synthesis (Hawaii Natural Energy Institute: HNEI, Stanford, and the National Renewable Energy Laboratory: NREL) and advanced materials and interfaces characterization (University of Nevada, Las Vegas: UNLV, and Lawrence Berkeley National Laboratory: LBNL), to accelerate the development of high efficiency and durable chalcopyrite materials for advanced photoelectrochemical (PEC) water splitting. Using this synergistic approach, we have successfully created new wide bandgap chalcopyrite photocathodes generating over 10 mA/cm 2 , developed innovative strategies to protect them from corrosion, and engineered novel integration methods to circumvent thin film materials mechanical, chemical and thermal incompatibility. In Task 1 “Modeling and synthesis of chalcopyrite photocathodes”, we expanded our library of wide bandgap chalcopyrites for PEC water splitting. With support from LLNL’s “Computational Materials Diagnostics and Optimization of PEC Devices”, LBNL’s “photophysical” and NREL’s “I-III-VI Compound Semiconductors for Water-Splitting” nodes, we investigated two new chalcopyrite candidates for PEC water splitting: Cu(In,Al)Se 2 and Cu(In,B)Se 2 . We also further developed ordered vacancy compounds, such as CuGa 3 Se 5 , with unprecedented durability during PEC waters splitting in acidic solutions. In Task 2 “Interfaces engineering for enhanced efficiency and durability”, we addressed both the non-ideal band-edge positions of chalcopyrites with respect to water redox potentials, as well as their chemical instability under PEC water splitting, with a buried-junctions approach. With help from NREL’s “High-Throughput Experimental Thin Film Combinatorial Capabilities” and “Corrosion Analysis of Materials” nodes, we engineered environmentally friendly n-type buffers, including Mn x Zn 1-x O, to adjust the chalcopyrite band-edge positions and achieved photovoltages as high as 925 mV. Also, we integrated non-precious catalytic-protecting layers, such as WO 3 , to enhance the water splitting long-term stability of chalcopyrite absorbers. Finally, in Task 3 “Hybrid photoelectrode device integration”, we proposed an innovative method to bond wide bandgap photocathodes onto narrow bandgap PV drivers at room temperature using conductive polymers. Our semi-monolithic approach addressed fundamental processing incompatibility issues, as both the photocathode and the PV driver are processed separately. Proof-of-concept whole-chalcopyrite tandems were obtained by consecutive exfoliation and transfer of fully integrated 1.85 eV CuGa 3 Se 5 and 1.13 eV CuInGaSe 2 stacks from their Mo/SLG substrates onto a new single FTO host substrate.
08 HYDROGEN↗
Galvanic Protection Of 2219 Al By Al/Li Powder
Coatings consisting of aluminum/lithium powders incorporated into acrylic resin found to protect panels of 2219 aluminum from corrosion by salt spray better than coating consisting of 2219 aluminum in same acrylic resin. Exact mechanism by which aluminum/lithium coatings protect against corrosion unknown, although galvanic mechanism suspected. These coatings (instead of chromium) applied to fasteners and bars to provide cathodic protection, both with and without impressed electrical current.
Daech, Alfred↗
Tests of NASA ceramic thermal barrier coating for gas-turbine engines
A NASA ceramic thermal barrier coating (TBC) system was tested by industrial and governmental organizations for a variety of aeronautical marine, and ground-based gas-turbine engine applications. This TBC is a two-layer system with a bond coating of nickel-chromium-aluminum-yttrium (Ni-16Cr-6Al-0.6Y, in wt %) and a ceramic coating of yttria stabilized zirconia (ZrO2-12Y2O3, in wt %). Tests (Liebert and Stenka, 1979) have been conducted to determine corrosion resistance, thermal protection, durability, thermal conductivity, and fatigue characteristics. The information presented covers some of the significant test results obtained on the first three items. The information also includes photographs of coated parts after tests, measurements of coating loss, amount of metal wall temperature reduction when the TBC is used, and extent of base metal corrosion.
Liebert, C. H.↗
Corrosion control at the Cape - Environment at Cape Kennedy ideal for corrosion.
Material corrosion control techniques, considering initial structure design, coatings application and protective coatings specifications
PROTECTIVE COATING↗
Repairing Chipped Silicide Coatings on Refractory Metal Substrates
The space shuttle orbiter s reaction control system (RCS) is a series of small thrusters that use hypergolic fuels to orient the orbiter in space. The RCS thrusters are constructed from a special niobium-based alloy -- the C-103. This alloy retains excellent mechanical properties from cryogenic temperature all the way up to 2,500 F (1,370 C). C-103 is susceptible to rapid oxidation at elevated temperatures. The authors have developed two methods to repair damaged R512a coatings on C-103. For the first repair technique, metal foundries, semiconductor manufacturers, and many other industries have developed and routinely use coatings that can easily be painted on metal to protect it from corrosion, including oxidation, to temperatures in excess of 2,500 F (1,370 C). This first repair technique is considered somewhat temporary. The second repair technique is based on using the native coating material of the RCS nozzles. the chipped area is ground out and a "green" R512a coating is applied to the repair area. Both repair techniques can be applied for moderate protection until the permanent laser-repair technique is available to the repair area.
Youngquist, Robert↗
Effects of service environments on aluminum-brazed titanium (ABTi)
Aluminum brazed titanium (ABTi) structures were evaluated during prolonged exposure to extreme environments: elevated temperature exposure to airline service fluids, hydraulic fluid, and seawater, followed by laboratory corrosion tests. Solid-face and perforated face honeycomb sandwich panel specimens, stressed panel assemblies, and faying surface brazed joints were tested. The corrosion resistance of ABTi is satisfactory for commercial airline service. Unprotected ABTi proved inherently resistant to attack by all of the extreme service aircraft environments except: seawater at 700 K (800 F) and above, dripping phosphate ester hydraulic fluid at 505 K (450 F), and a marine environment at ambient temperature. The natural oxides and deposits present on titanium surfaces in airline service provide protection against hot salt corrosion pitting. Coatings are required to protect titanium dripping phosphate ester fluid at elevated temperatures and to protect exposed acoustic honeycomb parts against corrosion in a marine environment.
Cotton, W. L.↗
Design new epoxy nanocomposite coatings based on metal vanadium oxy-phosphate M 0.5 VOPO 4 for anti-corrosion applications
Epoxy nanocomposite coatings are an essential way to protect petroleum storage tanks from corrosion. For this purpose, the new nanocomposite epoxy coatings (P-M/epoxy composites) have been successfully designed. The P-M/epoxy composites are based on the metal vanadium oxy-phosphate M 0.5 VOPO 4 (where M = Mg, Ni, and Zn). The function of P-M/epoxy composites as anti-corrosion coatings was explored using electrochemical and mechanical tests. Using electrochemical impedance spectroscopy (EIS), it has been noticed that the pore resistance and polarization resistance of the P-M/epoxy composites remain higher as compared to the neat epoxy. The P-M/epoxy composites have the greatest impact on the cathodic dis-bonded area and water absorption. Besides, P-M/epoxy composites exhibit a very high order of mechanical properties. Further, Mg 0.5 VOPO 4 has the greatest effect on the anti-corrosion properties of epoxy coating followed by Zn 0.5 VOPO 4 and Ni 0.5 VOPO 4 . All these properties lead to developing effective anti-corrosion coatings. Thus, the net result from this research work is highly promising and provides a potential for future works on the anti-corrosion coating.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Sputter-ion plating of coatings for protection of gas-turbine blades against high-temperature oxidation and corrosion
Considerable effort is being devoted to the development of overlay coatings for protecting critical components such as turbine blades against high-temperature oxidation, corrosion, and erosion damage in service. The most commercially advanced methods for depositing coatings are electron-beam evaporation and plasma spraying. Sputter-ion plating (SIP) offers a potentially cheaper and simpler alternative method for depositing overlays. Experimental work on SIP of Co-Cr-Al-Y and Ni-Cr-Al-Ti alloy coatings is described. Results are presented of metallographic assessment of these coatings, and of the results obtained from high-velocity testing using a gas-turbine simulator rig.
Coad, J. P.↗