The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion
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Kohl, F. J.↗
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Galvanic Liquid Applied Coating System For Protection of Embedded Steel Surfaces from Corrosion
Corrosion of reinforcing steel in concrete is an insidious problem facing Kennedy Space Center (KSC), other Government Agencies, and the general public. These problems include KSC launch support structures, highway bridge infrastructure, and building structures such as condominium balconies. Due to these problems, the development of a Galvanic Liquid Applied Coating System would be a breakthrough technology having great commercial value for the following industries: Transportation, Infrastructure, Marine Infrastructure, Civil Engineering, and the Construction Industry. This sacrificial coating system consists of a paint matrix that may include metallic components, conducting agents, and moisture attractors. Similar systems have been used in the past with varying degrees of success. These systems have no proven history of effectiveness over the long term. In addition, these types of systems have had limited success overcoming the initial resistance between the concrete/coating interface. The coating developed at KSC incorporates methods proven to overcome the barriers that previous systems could not achieve. Successful development and continued optimization of this breakthrough system would produce great interest in NASA/KSC for corrosion engineering technology and problem solutions. Commercial patents on this technology would enhance KSC's ability to attract industry partners for similar corrosion control applications.
Curran, Joseph↗
Environmentally Preferable Coatings for Structural Steel Project
The Ground Systems Development and Operations (GSDO) Program at NASA John F. Kennedy Space Center (KSC) has the primary objective of modernizing and transforming the launch and range complex at KSC to benefit current and future NASA programs along with other emerging users. Described a the "launch support and infrastructure modernization program" in the NASA Authorization Act of 2010, the GSDO Program will develop and implement shared infrastructure and process improvements to provide more flexible, affordable, and responsive capabilities to a multi-user community. In support of the GSDO Program, the objective of this project is to determine the feasibility of environmentally friendly corrosion resistant coatings for launch facilities and ground support equipment. The focus of the project is corrosion resistance and survivability with the goal to reduce the amount of maintenance required to preserve the performance of launch facilities while reducing mission risk. Number of facilities/structures with metallic structural and non-structural components in a highly corrosive environment. Metals require periodic maintenance activity to guard against the insidious effects of corrosion and thus ensure that structures meet or exceed design or performance life. The standard practice for protecting metallic substrates in atmospheric environments is the application of corrosion protective coating system.
Technology Portfolio System↗
Corrosion-Prevention Capabilities of a Water-Borne, Silicone-Based, Primerless Coating
Comparative tests have been performed to evaluate the corrosion-prevention capabilities of an experimental paint of the type described in Water-Borne, Silicone-Based, Primerless Paints, NASA Tech Briefs, Vol. 26, No. 11 (November 2002), page 30. To recapitulate: these paints contain relatively small amounts of volatile organic solvents and were developed as substitutes for traditional anticorrosion paints that contain large amounts of such solvents. An additional desirable feature of these paints is that they can be applied without need for prior application of primers to ensure adhesion. The test specimens included panels of cold-rolled steel, stainless steel 316, and aluminum 2024-T3. Some panels of each of these alloys were left bare and some were coated with the experimental water-borne, silicone-based, primerless paint. In addition, some panels of aluminum 2024-T3 and some panels of a fourth alloy (stainless steel 304) were coated with a commercial solvent-borne paint containing aluminum and zinc flakes in a nitrile rubber matrix. In the tests, the specimens were immersed in an aerated 3.5-weight-percent aqueous solution of NaCl for 168 hours. At intervals of 24 hours, the specimens were characterized by electrochemical impedance spectroscopy (EIS) and measurements of corrosion potentials. The specimens were also observed visually. As indicated by photographs of specimens taken after the 168-hour immersion (see figure), the experimental primerless silicone paint was effective in preventing corrosion of stainless steel 316, but failed to protect aluminum 2024-T3 and cold-rolled steel. The degree of failure was greater in the case of the cold-rolled steel. On the basis of visual observations, EIS, and corrosion- potential measurements, it was concluded that the commercial aluminum and zinc-filled nitrile rubber coating affords superior corrosion protection to aluminum 2024-T3 and is somewhat less effective in protecting stainless steel 304.
Calle, Luz Marina↗
Materials and processes for Shuttle engine, external tank, and Solid Rocket Booster
The paper deals with the materials and processes for three Space Shuttle elements: Space Shuttle Main Engines (SSME), the External Tank (ET), and the Solid Rocket Boosters (SRB), beginning with an overview of the materials selection, tracking and control system. SSME materials and processes are considered with emphasis on hydrogen environment embrittlement, LOX/GOX compatibility, stress corrosion cracking, and hydraulic fluid testing and qualification. The ET is examined with attention given to welding and fracture mechanics, and the thermal protection system. The SRB is discussed with emphasis on corrosion prevention, stress corrosion and fracture toughness, the integrated test bed for in situ corrosion protection verification, aluminum processing, and the thermal protection system.
Schwinghamer, R. J.↗
pH Sensitive Microcapsules for Delivery of Corrosion Inhibitors
A considerable number of corrosion problems can be solved by coatings. However, even the best protective coatings can fail by allowing the slow diffusion of oxygen and moisture to the metal surface. Corrosion accelerates when a coating delaminates. Often, the problems start when microscopic nicks or pits on the surface develop during manufacturing or through wear and tear. This problem can be solved by the incorporation of a self-healing function into the coating. Several new concepts are currently under development to incorporate this function into a coating. Conductive polymers, nanoparticles, and microcapsules are used to release corrosion-inhibiting ions at a defect site. The objective of this investigation is to develop a smart coating for the early detection and inhibition of corrosion. The dual function of this new smart coating system is performed by pH-triggered release microcapsules. The microcapsules can be used to deliver healing agents to terminate the corrosion process at its early stage or as corrosion indicators by releasing dyes at the localized corrosion sites. The dyes can be color dyes or fluorescent dyes, with or without pH sensitivity. Microcapsules were formed through the interfacial polymerization process. The average size of the microcapsules can be adjusted from 1 to 100 micron by adjusting the emulsion formula and the microcapsule forming conditions. A typical microcapsule size is around 10 microns with a narrow size distribution. The pH sensitivity of the microcapsule can also be controlled by adjusting the emulsion formula and the polymerization reaction time. Both corrosion indicator (pH indicator) and corrosion inhibitor containing microcapsules were formed and incorporated into paint systems. Test panels of selected steels and aluminum alloys were painted using these paints. Testing of compatibility between the microcapsule system and different paint systems are in progress. Initial experiments with the microcapsule containing paint show visible color changes at induced corrosion sites and improvement of corrosion protection. Further investigation of the performance of the coating using electrochemical techniques and long term exposure are currently underway.
Li, Wenyan↗
Polytetrafluoroethylene-Impregnated Anodization For Aluminum
Technical memorandum describes experiments on ability of two commercial coatings and of standard hard anodization to protect aluminum against corrosion. Both commercial coatings, Polylube and Tufram, polytetrafluoroethylene-impregnated anodizations. Standard hard-anodized coating found to provide greatest protection.
Danford, Merlin D.↗
Oceanic corrosion test of bare and zinc-protected aluminum alloys for seawater heat exchangers
Bare 3004 tubes, 7072 Alclad 3004 tubes, and bare and zinc diffusion treated 3003 extrusions from a brazed aluminum, plate-fin heat exchanger were exposed to 1.8 m/sec flowing seawater aboard an open ocean test facility moored 3.4 km off the southeast coast of Puerto Rico. After six months exposure, the average corrosion rates for most varieties of aluminum materials converged to a low value of 0.015 mm/yr (0.6 mils/yr). Pitting did not occur in bare 3003 and 3004 samples during the six month test. Pitting did occur to varying degrees in the Alclad and zinc diffusion treated material, but did not penetrate to the base metal. Biofouling countermeasures (intermittent chlorination and brushing) did not affect the corrosion rates to any significant extent. Intermittent chlorination at a level of 0.5 ppm for 28 minutes daily controlled microbiofouling of the samples but did not prevent the development of a macrobiofouling community in areas of the plumbing with low flow.
Sasscer, D. S.↗
Beryllium fluoride coating as a corrosion retardant for beryllium.
High temperature modified Be fluoride, rhombic tridymite, protects Be against aqueous corrosion
Odonnell, P. M.↗
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.↗
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.↗