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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↗

Launch Pad Coatings for Smart Corrosion Control

Corrosion is the degradation of a material as a result of its interaction with the environment. The environment at the KSC launch pads has been documented by ASM International (formerly American Society for Metals) as the most corrosive in the US. The 70 tons of highly corrosive hydrochloric acid that are generated by the solid rocket boosters during a launch exacerbate the corrosiveness of the environment at the pads. Numerous failures at the pads are caused by the pitting of stainless steels, rebar corrosion, and the degradation of concrete. Corrosion control of launch pad structures relies on the use of coatings selected from the qualified products list (QPL) of the NASA Standard 5008A for Protective Coating of Carbon Steel, Stainless Steel, and Aluminum on Launch Structures, Facilities, and Ground Support Equipment. This standard was developed to establish uniform engineering practices and methods and to ensure the inclusion of essential criteria in the coating of ground support equipment (GSE) and facilities used by or for NASA. This standard is applicable to GSE and facilities that support space vehicle or payload programs or projects and to critical facilities at all NASA locations worldwide. Environmental regulation changes have dramatically reduced the production, handling, use, and availability of conventional protective coatings for application to KSC launch structures and ground support equipment. Current attrition rate of qualified KSC coatings will drastically limit the number of commercial off the shelf (COTS) products available for the Constellation Program (CxP) ground operations (GO). CxP GO identified corrosion detection and control technologies as a critical, initial capability technology need for ground processing of Ares I and Ares V to meet Constellation Architecture Requirements Document (CARD) CxP 70000 operability requirements for reduced ground processing complexity, streamlined integrated testing, and operations phase affordability. Researchers at NASA's Corrosion Technology Laboratory at KSC are developing a smart, environmentally friendly coating system for early corrosion detection, inhibition, and self healing of mechanical damage without external intervention. This smart coating will detect and respond actively to corrosion and mechanical damage such as abrasion and scratches, in a functional and predictable manner, and will be capable of adapting its properties dynamically. This coating is being developed using corrosion sensitive microcapsules that deliver the contents of their core (corrosion inhibiting compounds, corrosion indicators, and self healing agents) on demand when corrosion or mechanical damage to the coating occurs.

Calle, Luz M.↗

A Multifunctional Coating for Autonomous Corrosion Control

This slide presentation reviews the effects of corrosion on various structures at the Kennedy Space Center, and the work to discover a corrosion control coating that will be autonomous and will indicate corrosion at an early point in the process. Kennedy Space Center has many environmental conditions that are corrosive: ocean salt spray, heat, humidity, sunlight and acidic exhaust from the Solid Rocket Boosters (SRBs). Presented is a chart which shows the corrosion rates of carbon steel at various locations. KSC has the highest corrosion rates with 42.0 mils/yr, leading the next highest Galeta Point Beach, in the Panama Canal Zone with 27 mils/yr corrosion. A chart shows the changes in corrosion rate with the distance from the ocean. The three types of corrosion protective coatings are described: barrier (passive), Barrier plus active corrosion inhibiting components, and smart. A smart coating will detect and respond actively to changes in its environment in a functional and predictable manner and is capable of adapting its properties dynamically. The smart coating uses microcapsules, particles or liquid drops coated in polymers, that can detect and control the corrosion caused by the environment. The mechanism for a pH sensitive microcapsule and the hydrophobic core microcapsule are demonstrated and the chemistry is reviewed. When corrosion begins, the microcapsule will release the contents of the core (indicator, inhibitor, and self healing agent) in close proximity to the corrosion. The response to a pH increase is demonstrated by a series of pictures that show the breakdown of the microcapsule and the contents release. An example of bolt corrosion is used, as an example of corrosion in places that are difficult to ascertain. A comparison of various coating systems is shown.

Calle, L. M.↗

Evaluation of Encapsulated Inhibitor for Autonomous Corrosion Protection

This work concerns the development of smart coating technologies based on microencapsulation for the autonomous control of corrosion. Microencapsulation allows the incorporation of corrosion inhibitors into coating which provides protection through corrosion-controlled release of these inhibitors.One critical aspect of a corrosion protective smart coating is the selection of corrosion inhibitor for encapsulation and comparison of the inhibitor function before and after encapsulation. For this purpose, a systematic approach is being used to evaluate free and encapsulated corrosion inhibitors by salt immersion. Visual, optical microscope, and Scanning Electron Microscope (with low-angle backscatter electron detector) are used to evaluate these inhibitors. It has been found that the combination of different characterization tools provide an effective method for evaluation of early stage localized corrosion and the effectiveness of corrosion inhibitors.

Autonomous↗

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↗

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↗

John F. Kennedy Space Center's Technology Development and Application 2006-2007 Report

Topics covered include: Reversible Chemochromic Hydrogen Detectors; Determining Trajectory of Triboelectrically Charged Particles, Using Discrete Element Modeling; Using Indium Tin Oxide To Mitigate Dust on Viewing Ports; High-Performance Polyimide Powder Coatings; Controlled-Release Microcapsules for Smart Coatings for Corrosion Applications; Aerocoat 7 Replacement Coatings; Photocatalytic Coatings for Exploration and Spaceport Design; New Materials for the Repair of Polyimide Electrical Wire Insulation; Commodity-Free Calibration; Novel Ice Mitigation Methods; Crack Offset Measurement With the Projected Laser Target Device; New Materials for Structural Composites and Protective Coatings; Fire Chemistry Testing of Spray-On Foam Insulation (SOFI); Using Aerogel-Based Insulation Material To Prevent Foam Loss on the Liquid-Hydrogen Intertank; Particle Ejection and Levitation Technology (PELT); Electrostatic Characterization of Lunar Dust; Numerical Analysis of Rocket Exhaust Cratering; RESOLVE Projects: Lunar Water Resource Demonstration and Regolith Volatile Characterization; Tribocharging Lunar Soil for Electrostatic Beneficiation; Numerically Modeling the Erosion of Lunar Soil by Rocket Exhaust Plumes; Trajectory Model of Lunar Dust Particles; Using Lunar Module Shadows To Scale the Effects of Rocket Exhaust Plumes; Predicting the Acoustic Environment Induced by the Launch of the Ares I Vehicle; Measuring Ultrasonic Acoustic Velocity in a Thin Sheet of Graphite Epoxy Composite; Hail Size Distribution Mapping; Launch Pad 39 Hail Monitor Array System; Autonomous Flight Safety System - Phase III; The Photogrammetry Cube; Bird Vision System; Automating Range Surveillance Through Radio Interferometry and Field Strength Mapping Techniques; Next-Generation Telemetry Workstation; GPS Metric Tracking Unit; and Space-Based Range.

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A Multifunctional Coating for Autonomous Corrosion Control

Corrosion is a destructive process that often causes failure in metallic components and structures. 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 control it. The multi-functionality of the coating is based on microencapsulation technology specifically designed for corrosion control applications. This design has, in addition to all the advantages of other existing microcapsules designs, the corrosion controlled release function that allows the delivery of corrosion indicators and inhibitors on demand only when and where they are needed. Corrosion indicators as well as corrosion inhibitors have been incorporated into the microcapsules, blended into several paint systems, and tested for corrosion detection and protection efficacy.

Calle, Luz M.↗

Corrosion 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 Control↗

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↗

Inkjet Printing of Conductive Carbon Nanotubes

Systems and methods for forming conductive materials. The conductive materials can be applied using a printer in single or multiple passes onto a substrate. The conductive materials are composed of electrical conductors such as carbon nanotubes (including functionalized carbon nanotubes and metal-coated carbon nanotubes), grapheme, a polycyclic aromatic hydrocarbon (e.g. pentacene and bisperipentacene), metal nanoparticles, an inherently conductive polymer (ICP), and combinations thereof. Once the conductive materials are applied, the materials are dried and sintered to form adherent conductive materials on the substrate. The adherent conductive materials can be used in applications such as damage detection, particle removal, and smart coating systems.

Roberson, Luke B.↗

Conductive Carbon Nanotube Inks for Use with Desktop Inkjet Printing Technology

Inkjet printing is a common commercial process. In addition to the familiar use in printing documents from computers, it is also used in some industrial applications. For example, wire manufacturers are required by law to print the wire type, gauge, and safety information on the exterior of each foot of manufactured wire, and this is typically done with inkjet or laser printers. The goal of this work was the creation of conductive inks that can be applied to a wire or flexible substrates via inkjet printing methods. The use of inkjet printing technology to print conductive inks has been in testing for several years. While researchers have been able to get the printing system to mechanically work, the application of conductive inks on substrates has not consistently produced adequate low resistances in the kilohm range. Conductive materials can be applied using a printer in single or multiple passes onto a substrate including textiles, polymer films, and paper. The conductive materials are composed of electrical conductors such as carbon nanotubes (including functionalized carbon nanotubes and metal-coated carbon nanotubes); graphene, a polycyclic aromatic hydrocarbon (e.g., pentacene and bisperipentacene); metal nanoparticles; inherently conductive polymers (ICP); and combinations thereof. Once the conductive materials are applied, the materials are dried and sintered to form adherent conductive materials on the substrate. For certain formulations, increased conductivity can be achieved by printing on substrates supported by low levels of magnetic field alignment. The adherent conductive materials can be used in applications such as damage detection, dust particle removal, smart coating systems, and flexible electronic circuitry. By applying alternating layers of different electrical conductors to form a layered composite material, a single homogeneous layer can be produced with improved electrical properties. It is believed that patterning alternate layers of different conductors may improve electrical pathways through alignment of the conductors and band gap optimization. One feature of this innovation is that flexible conductive traces could be accomplished with a conductive ink having a surface resistivity of less than 10 ohms/square. Another result was that a composite material comprising a mixture of carbon nanotubes and metallic nanoparticles could be applied by inkjet printing to flexible substrates, and the resulting applied material was one to two orders of magnitude more conductive than a material made by printing inks containing carbon nanotubes alone.

Roberson, Luke↗

Center Director's Discretionary Fund 2005 Annual Report

The FY 2005 CDDF projects were selected from the following spaceport and range technology and science areas: fluid system technologies; spaceport structures and materials; command, control, and monitoring technologies; and biological sciences (including support for environmental stewardship). The FY 2005 CDDF research projects involved development of the following: a) Capacitance-based moisture sensors to optimize plant growth in reduced gravity; b) Commodity-free calibration methods; c) Application of atmospheric plasma glow discharge to alter the surface properties of polymers for improved electrostatic dissipation characteristics; d) A wipe-on, wipe-off chemical process to remove lead oxides found in paint; e) A robust metabolite profiling platform for better understanding the "law" of biological regulation; f) An explanation of the excavation processes that occur when a jet of gas impinges on a bed of sand; g) "Smart coatings" to detect and control corrosion at an early stage to prevent further corrosion h) A model that can produce a reliable diagnosis of the quality of a software product; i) The formulation of advanced materials to meet system safety needs to minimize electrostatic charges, flammability, and radiation exposure; j) A lab-based instrument that uses the electro-optic Pockels effect to make static electric fields visible; k) A passive volatile organic compound (VOC) cartridge to filter, identify, and quantify VOCs flowing into or emanating from plant flight experiments.

Nurge, Mark↗

Recent Developments on Microencapsulation for Autonomous Corrosion Protection

This work concerns recent progress in the development of a multifunctional smart coating based on microencapsulation for the autonomous control of corrosion. Microencapsulation allows the incorporation of desired corrosion control functionalities, such as early corrosion detection and inhibition through corrosion controlled release of corrosion indicators and inhibitors, as well as self-healing agent release when mechanical damage occurs.While proof-of-concept results have been reported previously, more recent efforts have been concentrated in technical developments to improve coating compatibility, synthesis procedure scalability, as well as fine tuning the release property of encapsulated active agents.

Corrosion↗

Recent Developments on Autonomous Corrosion Protection Through Encapsulation

This paper concerns recent progress in the development of a multifunctional smart coating, based on microencapsulation, for the autonomous detection and control of corrosion. Microencapsulation has been validated and optimized to incorporate desired corrosion control functionalities, such as early corrosion detection and inhibition, through corrosion-initiated release of corrosion indicators and inhibitors, as well as self-healing agent release triggered by mechanical damage. While proof-of-concept results have been previously reported, more recent research and development efforts have concentrated on improving coating compatibility and synthesis procedure scalability, with a targeted goal of obtaining easily dispersible pigment-grade type microencapsulated materials. The recent progress has resulted in the development of pH-sensitive microparticles as a corrosion-triggered delivery system for corrosion indicators and inhibitors. The synthesis and early corrosion indication results obtained with coating formulations that incorporate these microparticles are reported. The early corrosion indicating results were obtained with color changing and with fluorescent indicators.

Autonomous↗

Carbon-Based Wear Coatings: Properties and Applications

The technical function of numerous engineering systems - such as vehicles, machines, and instruments - depends on the processes of motion and on the surface systems. Many processes in nature and technology depend on the motion and dynamic behavior of solids, liquids, and gases. Smart surface systems are essential because of the recent technological push toward higher speeds, loads, and operating temperatures; longer life; lighter weight and smaller size (including nanotechnology); and harsh environments in mechanical, mechatronic, and biomechanical systems. If proper attention is not given to surface systems, then vehicles, machines, instruments, and other technical systems could have short lives, consume excessive energy, experience breakdowns, result in liabilities, and fail to accomplish their missions. Surface systems strongly affect our national economy and our lifestyles. At the NASA Glenn Research Center, we believe that proper attention to surface systems, especially in education, research, and application, could lead to economic savings of between 1.3 and 1.6 percent of the gross domestic product. Wear coatings and surface systems continue to experience rapid growth as new coating and surface engineering technologies are discovered, more cost-effective coating and surface engineering solutions are developed, and marketers aggressively pursue, uncover, and exploit new applications for engineered surface systems in cutting tools and wear components. Wear coatings and smart surface systems have been used widely in industrial, consumer, automotive, aerospace, and biomedical applications. This presentation expresses the author's views of and insights into smart surface systems in wear coatings. A revolution is taking place in carbon science and technology. Diamond, an allotrope of carbon, joins graphite, fullerenes, and nanotubes as its major pure carbon structures. It has a unique combination of extreme properties: hardness and abrasion resistance; adhesion and friction; thermal conductivity; chemical and thermal inertness; corrosion and wear resistance; radiation resistance and biocompatibility; electronic, acoustic, and electrochemical characteristics; and environmental compatibility. These properties make diamond attractive for a wide range of diverse applications. In particular, chemical-vapor-deposited (CVD) diamond coatings offer a broad potential, since size and cost are not as limiting. The production of large, superhard diamond films or sheets at low cost make designer materials possible. This presentation is divided into two sections: properties and applications of hard coatings. The first section is concerned with the fundamental properties of the surfaces of CVD diamonds and related materials. The surface properties of hard coatings with favorable coefficients of friction (less than or equal to 0.1) and dimensional wear coefficients (less than or equal to 10(exp -6) cubic millimeters/N.m) in specific environments are discussed. The second section is devoted to applications. Examples of actual, successful applications and of potential challenging applications of the coatings.such as CVD diamond, diamondlike carbon, and cubic boron nitride-are described. Cutting tools coated with CVD diamond are of immediate commercial interest. Other applications, such as microelectromechanical systems (MEMS), valves, and bearings of CVD diamond, are being developed, but at a slow pace. There is a continually growing interest in commercializing diamondlike carbon for wear parts applications, such as biomedical parts and implants, forming dies, transport guides, magnetic tapes and disks, valves, and gears. Cubic boron nitride films are receiving attention because they can be used on tools to machine ferrous materials or on wear parts in sliding contact with ferrous materials.

Miyoshi, Kazuhisa↗

New Materials for Structural Composites and Protective Coatings

The objective of this Phase I project was to create novel conductive materials that are lightweight and strong enough for multiple ground support equipment and Exploration applications. The long-term goal is to combine these materials within specially designed devices to create composites or coatings with diagnostic capabilities, increased strength, and tunable properties such as transparency, electroluminescence, and fire resistance. One such technology application is a smart windows system. In such a system, the transmission of light through a window is controlled by electrical power. In the future, these materials may also be able to absorb sunlight and convert it into electrical energy to produce light, thereby creating a self-sufficient lighting system. This experiment, conducted in collaboration with the Georgia Institute of Technology, demonstrated enhancements in fabricating fiber materials from carbon nanotubes (CNT). These nanotubes were grown as forests in an ultra-high-purity chemical vapor deposition (CVD) furnace and then drawn, using novel processing techniques, into fibers and yarns that would be turned into filaments. This work was submitted to the Journal of Advanced Functional Materials. The CNT fibers were initially tested as filament materials at atmospheric pressure; however, even under high current loads, the filaments produced only random sparking. The CNT fibers were also converted into transparent, hydrophobic, and conductive sheets. Filament testing at low vacuum pressures is in progress, and the technology will be enhanced in 2008. As initial proof of the smart-windows application concept, the use of CNT sheets as composites/ protective coatings was demonstrated in collaboration with Nanocomp Technologies of Concord, New Hampshire.

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