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Refractory Materials for Flame Deflector Protection System Corrosion Control: Refractory Ceramics Literature Survey

Ceramics can be defmed as a material consisting of hard brittle properties produced from inorganic and nonmetallic minerals made by firing at high temperatures. These materials are compounds between metallic and nonmetallic elements and are either totally ionic, or predominately ionic but having some covalent character. This definition allows for a large range of materials, not all applicable to refractory applications. As this report is focused on potential ceramic materials for high temperature, aggressive exposure applications, the ceramics reviewed as part of this report will focus on refractory ceramics specifically designed and used for these applications. Ceramic materials consist of a wide variety of products. Callister (2000) 1 characterized ceramic materials into six classifications: glasses, clay products, refractories, cements, abrasives, and advanced ceramics. Figure 1 shows this classification system. This review will focus mainly on refractory ceramics and cements as in general, the other classifications are neither applicable nor economical for use in large structures such as the flame trench. Although much work has been done in advanced ceramics over the past decade or so, these materials are likely cost prohibitive and would have to be fabricated off-site, transported to the NASA facilities, and installed, which make these even less feasible. Although the authors reviewed the literature on advanced ceramic refractories 2 center dot 3 center dot 4 center dot 5 center dot 6 center dot 7 center dot 8 center dot 9 center dot 10 center dot 11 center dot 12 after the review it was concluded that these materials should not be ' the focus of this report. A review is in progress on materials and systems for prefabricated refractory ceramic panels, but this review is focusing more on typical refractory materials for prefabricated systems, which could make the system more economically feasible. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex. Refractory ceramics are used for a wide variety of applications. Figure 2 shows many ofthese applications, their life expectancy or requirement, and the exposure temperature for the refractory ceramic. Note that the exposure temperatures for refractory ceramics are very similar to the exposure conditions for specialty ceramics (rocket nozzles, space vehicle re-entry fields, etc.) and yet the life expectancy or requirement is relatively low. Currently NASA is repairing the refractory lining in the flame trench after every launch - although this is not a direct indication of low life expectancy, it does indicate that the current system may not be sufficiently durable to maximize economy. Better performing refractory ceramics are needed to improve the performance, economy, and safety during and after launches at the flame trenches at Kennedy Space Center (KSC). To achieve this goal a current study is underway to assess different refractory systems for possible use in the flame trenches at KSC. This report will target the potential applicability of refractory ceramics for use in the flame trenches. An overview of the different refractory ceramics will be provided (see Figure I). This will be followed with a brief description of the structure of refractory products, the properties and characteristics of different systems, the methodology for selecting refractories, and then a general design methodology. Based on these sections, future challenges and opportunities will be identified with the objective of improving the durability, performance, economy, and safety of the launch complex.

Calle, Luz Marina↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and de-icing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP (the Dept. of Defense's (DoD's) Environmental Security Technology Certification Program) demonstration effort.The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kilograms. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow-on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft de-icing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization. Abstract for Appendix A. Toxicology Report: Corrosion controls a significant problem for military equipment. Many surface treatment materials currently in use on items of military or aerospace materiel contain chromium (VI) as a component, a source of significant human health and environmental hazard. The formulation under evaluation contains no chromium. Most of the proposed components are low to moderate toxicity and are not a significant concern. Two of the formulation components are associated with some cancer hazard - 2-mercaptobenzothiazole and formaldehyde, but both find widespread use in industry and additional investigation is not required for this project.

Calle, Luz Marina↗

Corrosion-Activated Micro-Containers for Environmentally Friendly Corrosion Protective Coatings

This work concerns the development of environmentally friendly encapsulation technology, specifically designed to incorporate corrosion indicators, inhibitors, and self-healing agents into a coating, in such a way that the delivery of the indicators and inhibitors is triggered by the corrosion process, and the delivery of self-healing agents is triggered by mechanical damage to the coating. Encapsulation of the active corrosion control ingredients allows the incorporation of desired autonomous corrosion control functions such as: early corrosion detection, hidden corrosion detection, corrosion inhibition, and self-healing of mechanical damage into a coating. The technology offers the versatility needed to include one or several corrosion control functions into the same coating.The development of the encapsulation technology has progressed from the initial proof-of-concept work, in which a corrosion indicator was encapsulated into an oil-core (hydrophobic) microcapsule and shown to be delivered autonomously, under simulated corrosion conditions, to a sophisticated portfolio of micro carriers (organic, inorganic, and hybrid) that can be used to deliver a wide range of active corrosion ingredients at a rate that can be adjusted to offer immediate as well as long-term corrosion control. The micro carriers have been incorporated into different coating formulas to test and optimize the autonomous corrosion detection, inhibition, and self-healing functions of the coatings. This paper provides an overview of progress made to date and highlights recent technical developments, such as improved corrosion detection sensitivity, inhibitor test results in various types of coatings, and highly effective self-healing coatings based on green chemistry. The NASA Kennedy Space Centers Corrosion Technology Lab at the Kennedy Space Center in Florida, U.S.A. has been developing multifunctional smart coatings based on the microencapsulation of environmentally friendly corrosion indicators, inhibitors and self-healing agents. This allows the incorporation of autonomous corrosion control functionalities, such as corrosion detection and inhibition as well as the self-healing of mechanical damage, into coatings. This paper presents technical details on the characterization of inhibitor-containing particles and their corrosion inhibitive effects using electrochemical and mass loss methods.Three organic environmentally friendly corrosion inhibitors were encapsulated in organic microparticles that are compatible with desired coatings. The release of the inhibitors from the microparticles in basic solution was studied. Fast release, for immediate corrosion protection, as well as long-term release for continued protection, was observed.The inhibition efficacy of the inhibitors, incorporated directly and in microparticles, on carbon steel was evaluated. Polarization curves and mass loss measurements showed that, in the case of 2MBT, its corrosion inhibition effectiveness was greater when it was delivered from microparticles.

Corrosion Control↗

A 20 Year Lifecycle Study for Launch Facilities at the Kennedy Space Center

The lifecycle cost analysis was based on corrosion costs for the Kennedy Space Center's Launch Complexes and Mobile Launch Platforms. The first step in the study involved identifying the relevant assets that would be included. Secondly, the identification and collection of the corrosion control cost data for the selected assets was completed. Corrosion control costs were separated into four categories. The sources of cost included the NASA labor for civil servant personnel directly involved in overseeing and managing corrosion control of the assets, United Space Alliance (USA) contractual requirements for performing planned corrosion control tasks, USA performance of unplanned corrosion control tasks, and Testing and Development. Corrosion control operations performed under USA contractual requirements were the most significant contributors to the total cost of corrosion. The operations include the inspection of the pad, routine maintenance of the pad, medium and large scale blasting and repainting activities, and the repair and replacement of structural metal elements. Cost data was collected from the years between 2001 and 2007. These costs were then extrapolated to future years to calculate the 20 year lifecycle costs.

Kolody, Mark R.↗

NASA's Corrosion Technology Laboratory at the Kennedy Space Center: Anticipating, Managing, and Preventing Corrosion

The marine environment at NASAs Kennedy Space Center (KSC) has been documented by ASM International (formerly American Society for Metals) as the most corrosive in North America. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pads were rendered even more severe by the highly corrosive hydrochloric acid (HCl) generated by the solid rocket boosters (SRBs). Numerous failures at the launch pads are caused by corrosion. The structural integrity of ground infrastructure and flight hardware is critical to the success, safety, cost, and sustainability of space missions. NASA has over fifty years of experience dealing with unexpected failures caused by corrosion and has developed expertise in corrosion control in the launch and other environments. The Corrosion Technology Laboratory at KSC evolved, from what started as an atmospheric exposure test site near NASAs launch pads, into a capability that provides technical innovations and engineering services in all areas of corrosion for NASA, external partners, and customers.This paper provides a chronological overview of NASAs role in anticipating, managing, and preventing corrosion in highly corrosive environments. One important challenge in managing and preventing corrosion involves the detrimental impact on humans and the environment of what have been very effective corrosion control strategies. This challenge has motivated the development of new corrosion control technologies that are more effective and environmentally friendly. Strategies for improved corrosion protection and durability can have a huge impact on the economic sustainability of human spaceflight operations.

Corrosion Control↗

Release Properties and Electrochemical Characterization of Encapsulated Corrosion Inhibitors for Environmentally Friendly Smart Coatings

The NASA Kennedy Space Center's Corrosion Technology Lab at the Kennedy Space Center in Florida, U.S.A. has been developing multifunctional smart coatings based on the microencapsulation of environmentally friendly corrosion indicators, inhibitors and self-healing agents. This allows for the incorporation of autonomous corrosion control functionalities, such as corrosion detection and inhibition as well as the self-healing of mechanical damage, into coatings. This paper presents technical details on the characterization of inhibitor-containing particles and their corrosion inhibitive effects using electrochemical and mass loss methods. Three organic environmentally friendly corrosion inhibitors were encapsulated in organic microparticles that are compatible with desired coatings. The total inhibitor content and the release of one of the inhibitors from the microparticles in basic solution was measured. Particles with inhibitor contents of up 60 wt% were synthesized. Fast release, for immediate corrosion protection, as well as long-term release for continued protection, was observed. The inhibition efficacy of the inhibitors, both as the pure materials and in microparticles, on carbon steel was evaluated. Polarization curves and mass loss measurements showed that, in the case of 2MBT, its corrosion inhibition effectiveness was greater when it was delivered from microparticles.

Coatings↗

NASA's Corrosion Technology Laboratory at the Kennedy Space Center: Anticipating, Managing, and Preventing Corrosion

Corrosion is the degradation of a material that results from its interaction with the environment. The marine environment at NASAs Kennedy Space Center (KSC) has been documented by ASM International (formerly American Society for Metals) as the most corrosive in the United States. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pads were rendered even more severe by the 70 tons of highly corrosive hydrochloric acid that were generated by the solid rocket boosters. Numerous failures at the launch pads are caused by corrosion.The structural integrity of ground infrastructure and flight hardware is critical to the success, safety, cost, and sustainability of space missions. As a result of fifty years of experience with launch and ground operations in a natural marine environment that is highly corrosive, NASAs Corrosion Technology Laboratory at KSC is a major source of corrosion control expertise in the launch and other environments. Throughout its history, the Laboratory has evolved from what started as an atmospheric exposure facility near NASAs launch pads into a world-wide recognized capability that provides technical innovations and engineering services in all areas of corrosion for NASA and external customers.This presentation will provide a historical overview of the role of NASAs Corrosion Technology in anticipating, managing, and preventing corrosion. One important challenge in managing and preventing corrosion involves the detrimental impact on humans and the environment of what have been very effective corrosion control strategies. This challenge has motivated the development of new corrosion control technologies that are more effective and environmentally friendly. Strategies for improved corrosion protection and durability can have a huge impact on the economic sustainability of human spaceflight operations.

Corrosion↗

Microencapsulation Technologies for Corrosion Protective Coating Applications

Microencapsulation technologies for functional smart Coatings for autonomous corrosion control have been a research area of strong emphasis during the last decade. This work concerns the development of pH sensitive micro-containers (microparticles and microcapsules) for autonomous corrosion control. This paper presents an overview of the state-of-the-art in the field of microencapsulation for corrosion control applications, as well as the technical details of the pH sensitive microcontainer approach, such as selection criteria for corrosion indicators and corrosion inhibitors; the development and optimization of encapsulation methods; function evaluation before and after incorporation of the microcontainers into coatings; and further optimization to improve coating compatibility and performance.

Microencapsulation↗

Superhydrophobic Post Treatment and Coating Extenders for Improved Asset Sustainability

Launch structures, hardware, and ground support equipment, at NASA's John F. Kennedy Space Center in Florida, are exposed to a highly corrosive natural coastal marine environment. In addition, during launches, rocket exhaust deposition is also highly corrosive. Superhydrophobic coatings are being considered for additional corrosion protection on existing structures to enhance corrosion resistance and add an additional layer of protection against harsh environmental elements. These coatings have come into their own recently, and are now being investigated as corrosion protective coatings due to their water repelling capability. These coatings can be used on existing coatings, newly coated materials, or used on bare substrates. The coatings are not suitable for permanent corrosion protection, but can be used where additional corrosion control is desired or only when temporary corrosion control is needed, such as in hardware sitting on a launch pad for 30-45 days prior to a launch. In this study, superhydrophobic coatings were applied on various coated and uncoated substrates and exposed to the spaceport environment for various times up to 60 days. This paper highlights the current results of the superhydrophobic coatings performance evaluated by X-ray photoelectron spectroscopy, and contact angle measurements.

Coating↗

Thermal control system corrosion study

During the development of an expert system for autonomous control of the Space Station Thermal Control System (TCS), the thermal performance of the Brassboard TCS began to gradually degrade. This degradation was due to filter clogging by metallic residue. A study was initiated to determine the source of the residue and the basic cause of the corrosion. The investigation focused on the TCS design, materials compatibility, Ames operating and maintenance procedures, and chemical analysis of the residue and of the anhydrous ammonia used as the principal refrigerant. It was concluded that the corrosion mechanisms involved two processes: the reaction of water alone with large, untreated aluminum parts in a high pH environment and the presence of chlorides and chloride salts. These salts will attack the aluminum oxide layer and may enable galvanic corrosion between the aluminum and the more noble stainless steel and other metallic elements present. Recommendations are made for modifications to the system design, the materials used, and the operating and maintenance procedures, which should largely prevent the recurrence of these corrosion mechanisms.

Yee, Robert↗

Characterization of Encapsulated Corrosion Inhibitors for Environmentally Friendly Smart Coatings

The NASA Kennedy Space Center's Corrosion Technology Lab at the Kennedy Space Center in Florida, U.S.A. has been developing multifunctional smart coatings based on the microencapsulation of environmentally friendly corrosion indicators, inhibitors and self-healing agents. This allows the incorporation of autonomous corrosion control functionalities, such as corrosion detection and inhibition as well as the self-healing of mechanical damage, into coatings. This paper presents technical details on the characterization of inhibitor-containing particles and their corrosion inhibitive effects using electrochemical and mass loss methods. Three organic environmentally friendly corrosion inhibitors were encapsulated in organic microparticles that are compatible with desired coatings. The release of the inhibitors from the microparticles in basic solution was studied. Fast release, for immediate corrosion protection, as well as long-term release for continued protection, was observed. The inhibition efficacy of the inhibitors, incorporated directly and in microparticles, on carbon steel was evaluated. Polarization curves and mass loss measurements showed that, in the case of 2MBT, its corrosion inhibition effectiveness was greater when it was delivered from microparticles.

Corrosion↗

Corrosion Activities at the NASA Kennedy Space Center

This report documents summer faculty fellow efforts in the corrosion test bed at the NASA Kennedy Space Center. During the summer of 2002 efforts were concentrated on three activities: a short course on corrosion control for KSC personnel, evaluation of commercial wash additives used for corrosion control on Army aircraft, and improvements in the testing of a new cathodic protection system under development at KSC.

Heidersbach, Robert H.↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Alternatives to Hexavalent Chromium, Controlled Re↗

Smart Multifunctional Coatings for Corrosion Detection and Control in the Aerospace Industry

Nearly all metals and their alloys are subject to corrosion that causes them to lose their structural integrity or other critical functionality. It is essential to detect corrosion when it occurs, and preferably at its early stage, so that action can be taken to avoid structural damage or loss of function. Protective coatings are the most commonly used method of corrosion control. However, progressively stricter environmental regulations have resulted in the ban of many commercially available corrosion protective coatings due to the harmful effects of their solvents or corrosion inhibitors. This work concerns the development of a multifunctional, smart coating for the autonomous control of corrosion. This coating is being developed to have the inherent ability to detect the chemical changes associated with the onset of corrosion and respond autonomously to indicate it and control it.

Corrosion↗

Smart Coatings for Corrosion Protection

Nearly all metals and their alloys are subject to corrosion that causes them to lose their structural integrity or other critical functionality. It is essential to detect corrosion when it occurs, and preferably at its early stage, so that action can be taken to avoid structural damage or loss of function. Protective coatings are the most commonly used method of corrosion control. However, progressively stricter environmental regulations have resulted in the ban of many commercially available corrosion protective coatings due to the harmful effects of their solvents or corrosion inhibitors. This work concerns the development of a multifunctional, smart coating for the autonomous control of corrosion. This coating is being developed to have the inherent ability to detect the chemical changes associated with the onset of corrosion and respond autonomously to indicate it and control it.

Coatings↗

Pre-Demonstration Development of Controlled-Release Corrosion Inhibitors and Healing Agents as Alternatives to Hexavalent Chromium

This Limited Scope Study was directed to achieve the following objectives: (1) Scale-up of materials that can meet MIL-PRF-23377 (solvent-based primer). (2) Provide evidence of resistance to aircraft alkaline cleaners and deicing fluids. (3) Provide formulation for initial ecological and toxicity screening. (4) Submit an interim report that will provide the basis for a future ESTCP demonstration effort. The encapsulation procedure for two corrosion inhibitors was scaled up from lab scale to 2.0 kg. This scale will accommodate high volume production of coatings with encapsulated corrosion inhibitors for large surface areas during a follow on ESTCP demonstration effort. Test results provided evidence of resistance to alkaline cleaners and aircraft deicing fluids and compliance with MIL-PRF-23377. All the MIL-PRF-23377 requirements were met with the exception of the adhesion requirement, in top coated panels, and the flexibility requirement. Work on solving these two problems will be done prior to validation and demonstration of the technology. An initial ecological and toxicity screening identified several factors that were not critical to the acceptance of the encapsulated corrosion inhibitor. This new technology will lead to environmentally friendly alternatives to hexavalent chromium that will enable DoD to protect its assets. Field demonstration, licensing, qualification, and commercialization will allow its real world utilization.

Alternatives to Hexavalent Chromium↗

Development and Assessment of Deployed Sensors and Technologies Supporting Molten Salt Loop Operations

During FY24, Argonne conducted a variety of activities to develop and assess new monitoring and control technologies towards enabling long-duration operations of molten salt reactor systems. The first objective of the work completed this year was to deploy technologies capable of reliably and rapidly monitoring the operational health of a molten salt loop. To achieve this, the project focused on specific tasks, including: (1) electroanalytical technique development for use in deployed sensors, and (2) operations of sensors on the Facility to Alleviate Salt Technology Risks (FASTR) loop at Oak Ridge National Laboratory. The second objective of the work this year focused on creating a pumped actinide flow loop to enable long-duration salt chemistry and corrosion studies using uranium-bearing fuel salts. Toward that end, we designed and procured a loop capable of being installed into a radiological glovebox at Argonne. A corrosion control system was also designed for integration into this loop. These combined systems will enable the feasibility of corrosion control and management systems to be investigated with complex chloride fuel salt mixtures.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗