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At least 109 records · Page 6

Localized corrosion of high performance metal alloys in an acid/salt environment

Various vacuum jacketed cryogenic supply lines at the Space Shuttle launch site at Kennedy Space Center use convoluted flexible expansion joints. The atmosphere at the launch site has a very high salt content, and during a launch, fuel combustion products include hydrochloric acid. This extremely corrosive environment has caused pitting corrosion failure in the thin walled 304L stainless steel flex hoses. A search was done to find a more corrosion resistant replacement material. The study focussed on 19 metal alloys. Tests which were performed include electrochemical corrosion testing, accelerated corrosion testing in a salt fog chamber, and long term exposure at a beach corrosion testing site. Based on the results of these tests, several nickel based alloys were found to have very high resistance to this corrosive environment. Also, there was excellent agreement between the electrochemical tests and the actual beach exposure tests. This suggests that electrochemical testing may be useful for narrowing the field of potential candidate alloys before subjecting samples to long term beach exposure.

Macdowell, L. G.↗

Production of mullite fibers

Disclosed here is a process for making mullite fibers wherein a hydrolizable silicon compound and an aluminum compound in the form of a difunctional aluminum chelate are hydrolized to form sols using water and an alcohol with a catalytic amount of hydrochloric acid. The sols are mixed in a molar ratio of aluminum to silicon of 3 to 1 and, under polycondensation conditions, a fibrous gel is formed. From this gel the mullite fibers can be produced.

Tucker, Dennis S.↗

Metal etching composition

The present invention is directed to a chemical etching composition for etching metals or metallic alloys. The composition includes a solution of hydrochloric acid, phosphoric acid, ethylene glycol, and an oxidizing agent. The etching composition is particularly useful for etching metal surfaces in preparation for subsequent fluorescent penetrant inspection.

Otousa, Joseph E.↗

Fourier transform infrared studies of the interaction of HCl with model polar stratospheric cloud films

Heterogeneous reactions involving hydrochloric acid adsorbed on the surfaces of polar stratospheric clouds (PSCs) are postulated to contribute to polar ozone loss. Using FTIR spectroscopy to probe the condensed phase, we have examined the interaction of HCl with ice and nitric acid trihydrate (NAT) films representative of types II and I PSCs, respectively. For HCl pressures in the range of 10 exp -7 to 10 exp -5 Torr, our FTIR studies show that a small amount of crystalline HCl-6H2O formed on or in ice at 155 K. However, for higher HCl pressures, we observed that the entire film of ice rapidly converted into an amorphous 4:1 H2O:HCl mixture. From HCl-uptake experiments with P(HCl) = 8 x 10 exp -7 Torr, we estimate roughly that the diffusion coefficient of HCl in ice is around 2 x 10 exp -12 sq cm/s at 158 K. For higher temperatures more closely approximating those found in the stratosphere, we were unable to detect bulk HCl uptake by ice. Indirect evidence suggests that HCl adsorption onto the surface of model PSC films inhibited the evaporation of both ice and NAT by 3-5 K.

Koehler, Birgit G.↗

Chlorine chemistry on polar stratospheric cloud particles in the Arctic winter

Simultaneous in situ measurements of hydrochloric acid (HCl) and chlorine monoxide (ClO) in the Arctic winter vortex showed large HCl losses of up to 1 ppbv, which were correlated with high ClO levels of up to 1.4 ppbv. Air parcel trajectory analysis identified that this conversion of inorganic chlorine occurred at air temperatures of less than 196 -/+ 4 kelvin. High ClO was always accompanied by loss of HCl mixing ratios equal to 1/2(ClO+ 2Cl2O2). These data indicate that the heterogeneous reaction HCl + ClONO2 - Cl2 + HNO3 on particles of polar stratospheric clouds establishes the chlorine partitioning, which, contrary to earlier notions, begins with an excess of ClONO2, not HCl.

Webster, C. R.↗

Sulfur, Chlorine, and Flourine Degassing and Atmospheric Loading by the 1783 - 1784 AD Laki (Skaftar Fires) Eruption in Iceland

The 1783-1784 Laki tholeiitic basalt fissure eruption in Iceland was one of the greatest atmospheric pollution events of the past 250 years, with widespread effects in the northern hemisphere. The degassing history and volatile budget of this event are determined by measurements of pre-eruption and residual contents of sulfur, chlorine, and fluorine in the products of all phases of the eruption. In fissure eruptions such as Laki, degassing occurs in two stages: by explosive activity or lava fountaining at the vents, and from the lava as it flows away from the vents. Using the measured sulfur concentrations in glass inclusions in phenocrysts and in groundmass glasses of quenched eruption products, we calculate that the total accumulative atmospheric mass loading of sulfur dioxide was 122 Mt over a period of 8 months. This volatile release is sufficient to have generated approximately 250 Mt of H2SO4 aerosols, an amount which agrees with an independent estimate of the Laki aerosol yield based on atmospheric turbidity measurements. Most of this volatile mass (approximately 60 wt.%) was released during the first 1.5 months of activity. The measured chlorine and fluorine concentrations in the samples indicate that the atmospheric loading of hydrochloric acid and hydrofluoric acid was approximately 7.0 and 15.0 Mt, respectively. Furthermore, approximately 75% of the volatile mass dissolved by the Laki magma was released at the vents and carried by eruption columns to altitudes between 6 and 13 km. The high degree of degassing at the vents is attributed to development of a separated two-phase flow in the upper magma conduit, and implies that high-discharge basaltic eruptions such as Laki are able to loft huge quantities of gas to altitudes where the resulting aerosols can reside for months, or even 1-2 years. The atmospheric volatile contribution due to subsequent degassing of the Laki lava flow is only 18 wt.% of the total dissolved in the magma, and these emissions were confined to the lowest regions of the troposhere and therefore important only over Iceland. This study indicates that determination of the amount of sulfur degassed from the Laki magma batch by measurements of sulfur in the volcanic products (the petrologic method) yields a result which is sufficient to account for the mass of aerosols estimated by other methods.

Thordarson, T.↗

Electron and Light Microscopy Techniques Suitable for Studying Fatigue Damage in a Crystallized Glass Ceramic

The crystals of Pyroceram are randomly oriented and highly reflective so that standard microscopy techniques are not satisfactory for studying this material. Standard replicating procedures proved difficult to use. New microscopy techniques and procedures have therefore been developed. A method for locating, orienting, and identifying specific areas to be viewed with an electron microscope is described. This method not require any special equipment. Plastic replicas were found to be unsatisfactory because of their tendency to adhere to Pryoceram. This caused them to tear when released or resulted in artifacts. Preshadowed silicon monoxide replicas were satisfactory but required a releasing agent. A method of depositing the releasing agent is described. To polish specimens without evidence of fire-polishing, it was found necessary to use a vibratory polishing technique. Chrome oxide was used as the abrasive and either water or kerosene as the lubricant. Vibratory polishing is extremely slow, but surfaces so polished show no evidence of fire polishing, even when examined by electron microscopy. The most satisfactory etching process used for Pyroceram 9608 consisted of a primary etch of 5 milliliters of hydrochloric acid (concentrated), 5 milliliters of hydrogen fluoride (45 percent), and 45 milliliters of water, and a secondary etch with methyl alcohol replacing the water. Best results were obtained with total etching times from 25 to 30 seconds. Staining of the Pyroceram surface with a Sanford's marker was found to be an expedient way to reduce the glare of reflected light.

Harrell, Shelley↗

Passive, Direct-Read Monitoring System for Selective Detection and Quantification of Hydrogen Chloride

Monitoring the exposure of an employee to hydrogen chloride or hydrochloric acid in the presence of other acids has been a challenge to the industrial hygiene community. The capability of a device to differentiate the levels of acid vapors would allow for more accurate determinations of exposure and therefore improved occupational health. In this work, a selective direct-read colorimetric badge system was validated for Short Term Exposure Limit (STEL) monitoring of hydrogen chloride. The passive colorimetric badge system consists of a direct reading badge and a color scale. The badge has a coated indicator layer with a diffusive resistance in the shape of an exclamation mark. An exclamation mark will appear if hydrogen chloride is present in the atmosphere at concentrations at or above 2.0 ppm. By using the color scale, the intensity of the color formed on the badge can be further quantified up to 25 ppm. The system was validated according to a protocol based on the NIOSH Protocol for the Evaluation of Passive Monitors. The badge was exposed to relative humidities ranging from 11% to 92%, temperatures ranging from 7 C to 400 C and air velocities ranging from 5 cm/sec to 170 cm/sec. All experiments were conducted in a laboratory vapor generation system. Hydrofluoric acid, nitric acid, sulfuric acid, chlorine, hydrogen sulfide and organic acids showed no effect on the performance of the hydrogen chloride monitoring system. The passive badge and color scale system exceeded the accuracy requirements as defined by NIOSH. At ambient conditions, the mean coefficient of variation was 10.86 and the mean bias was 1.3%. This data was presented previously at the American Industrial Hygiene Conference and Exposition in Toronto, Canada in June 1999.

Chapman, K. B.↗

New Method Developed To Purify Single Wall Carbon Nanotubes for Aerospace Applications

Single wall carbon nanotubes have attracted considerable attention because of their remarkable mechanical properties and electrical and thermal conductivities. Use of these materials as primary or secondary reinforcements in polymers or ceramics could lead to new materials with significantly enhanced mechanical strength and electrical and thermal conductivity. Use of carbon-nanotube-reinforced materials in aerospace components will enable substantial reductions in component weight and improvements in durability and safety. Potential applications for single wall carbon nanotubes include lightweight components for vehicle structures and propulsion systems, fuel cell components (bipolar plates and electrodes) and battery electrodes, and ultra-lightweight materials for use in solar sails. A major barrier to the successful use of carbon nanotubes in these components is the need for methods to economically produce pure carbon nanotubes in large enough quantities to not only evaluate their suitability for certain applications but also produce actual components. Most carbon nanotube synthesis methods, including the HiPCO (high pressure carbon monoxide) method developed by Smalley and others, employ metal catalysts that remain trapped in the final product. These catalyst impurities can affect nanotube properties and accelerate their decomposition. The development of techniques to remove most, if not all, of these impurities is essential to their successful use in practical applications. A new method has been developed at the NASA Glenn Research Center to purify gram-scale quantities of single wall carbon nanotubes. This method, a modification of a gas phase purification technique previously reported by Smalley and others, uses a combination of high-temperature oxidations and repeated extractions with nitric and hydrochloric acid. This improved procedure significantly reduces the amount of impurities (catalyst and nonnanotube forms of carbon) within the nanotubes, increasing their stability significantly. The onset of decomposition of the purified nanotubes (determined by thermal gravimetric analysis in air) is more than 300 C higher than that of the crude nanotubes. Transmission electron microscopy analysis of nanotubes purified by this method reveals near complete removal of iron catalyst particles. Analysis of the nanotubes using inductively coupled plasma spectroscopy revealed that the iron content of the nanotubes was reduced from 22.7 wt% in the crude nanotubes to less than 0.02 wt%. X-ray photoelectron spectroscopy revealed a decrease in iron content after purification as well as an increase in oxygen content due to the formation of carboxylic acid groups on the surface of the nanotubes. Nanotubes purified by this improved method can be readily dispersed in common organic solvents, in particular N,N-dimethylformamide, using prolonged ultrasonic treatment. These dispersions can then be used to incorporate single wall carbon nanotubes into polymer films.

Lebron, Marisabel↗

The Connection between Model Performance on the CCMVal Transport Diagnostics and Simulated Sensitivity of Ozone to Chlorine Change

The chemistry climate models that contributed simulations for past and future ozone evolution to the 2010 Scientific Assessment of Ozone Depletion were subject to extensive evaluation by the SPARC (Stratospheric Processes and their Role in Climate) CCMVal (Chemistry-Climate Model Validation) activity. The sensitivity of ozone to changes in composition and climate varies among the models, but the relationship between these variations and the model evaluations of CCMVal is not obvious. We have learned that the transport evaluation can be used to interpret the comparisons between observed and simulated columns of chlorine reservoirs, hydrochloric acid (HCl) and chlorine nitrate (ClONO2); these comparisons were part of the CCMVal evaluation of chemistry. The simulations with best performance on the transport diagnostics most faithfully reproduce the evolution and seasonal variation of the chlorine reservoirs as observed at NDACC (Network for Detection of Atmospheric Composition Change) stations (NyAlesund 78.9N, Kiruna 67.8N, Harestua 60.2N, Jungfraujoch 46.6N, Toronto 43.6N, Kitt Peak 31.9N, Izana 28.3N, Mauna Loa 19.5N, Lauder 45S and Arrival Heights 77.8S). In the simulations, the HCl in the lower stratosphere depends on total inorganic chlorine (Cly) and partitioning between HCl and ClON02. Total inorganic chlorine depends on the fractional release of chlorine from source gases, and ratio of ClON02 to HCl is inversely dependent on methane and varies quadratically with ozone. Simulated HCl from various models may agree with observations even though Cly is in error, partitioning is in error, or both. Simulated ozone sensitivity to chlorine is shown to be greater for models that produce larger values of chlorine nitrate for background chlorine levels, and vice versa. Comparisons with the NDACC data show why the models with 'best' transport have similar sensitivity to chlorine change. The realistic evolution of the simulated HCl and ClONO2 columns suggests realistic levels of Cly in the lower atmosphere. In addition, the wide range values for the sensitivity of ozone to chlorine obtained from the CCMVal simulations is explained by the wide range in lower atmospheric columns of ClONO2 and the concomitant wide range of levels for chlorine monoxide.

Douglass, Anne↗

Soft-Bake Purification of SWCNTs Produced by Pulsed Laser Vaporization

The "soft-bake" method is a simple and reliable initial purification step first proposed by researchers at Rice University for single-walled carbon nanotubes (SWCNT) produced by high-pressure carbon mon oxide disproportionation (HiPco). Soft-baking consists of annealing as-produced (raw) SWCNT, at low temperatures in humid air, in order to degrade the heavy graphitic shells that surround metal particle impurities. Once these shells are cracked open by the expansion and slow oxidation of the metal particles, the metal impurities can be digested through treatment with hydrochloric acid. The soft-baking of SWCNT produced by pulsed-laser vaporization (PLV) is not straightforward, because the larger average SWCNT diameters (.1.4 nm) and heavier graphitic shells surrounding metal particles call for increased temperatures during soft-bake. A part of the technology development focused on optimizing the temperature so that effective cracking of the graphitic shells is balanced with maintaining a reasonable yield, which was a critical aspect of this study. Once the ideal temperature was determined, a number of samples of raw SWCNT were purified using the soft-bake method. An important benefit to this process is the reduced time and effort required for soft-bake versus the standard purification route for SWCNT. The total time spent purifying samples by soft-bake is one week per batch, which equates to a factor of three reduction in the time required for purification as compared to the standard acid purification method. Reduction of the number of steps also appears to be an important factor in improving reproducibility of yield and purity of SWCNT, as small deviations are likely to get amplified over the course of a complicated multi-step purification process.

Yowell, Leonard↗

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.↗

Exfoliation of Hexagonal Boron Nitride via Ferric Chloride Intercalation

Sodium fluoride (NaF) was used as an activation agent to successfully intercalate ferric chloride (FeCl3) into hexagonal boron nitride (hBN). This reaction caused the hBN mass to increase by approx.100 percent, the lattice parameter c to decrease from 6.6585 to between 6.6565 and 6.6569 Ǻ, the x-ray diffraction (XRD) (002) peak to widen from 0.01deg to 0.05deg of the full width half maximum value, the Fourier transform infrared (FTIR) spectrum's broad band (1277/cm peak) to change shape, and new FTIR bands to emerge at 3700 to 2700 and 1600/cm. This indicates hBN's structural and chemical properties are significantly changed. The intercalated product was hygroscopic and interacted with moisture in the air to cause further structural and chemical changes (from XRD and FTIR). During a 24-h hold at room temperature in air with 100 percent relative humidity, the mass increased another 141 percent. The intercalated product, hydrated or not, can be heated to 750 C in air to cause exfoliation. Exfoliation becomes significant after two intercalation-air heating cycles, when 20-nm nanosheets are commonly found. Structural and chemical changes indicated by XRD and FTIR data were nearly reversed after the product was placed in hydrochloric acid (HCl), resulting in purified, exfoliated, thin hBN products.

Hung, Ching-cheh↗

The Messy Aerosol Submodel MADE3 (v2.0b): Description and a Box Model Test

We introduce MADE3 (Modal Aerosol Dynamics model for Europe, adapted for global applications, 3rd generation), an aerosol dynamics submodel for application within the MESSy framework (Modular Earth Submodel System). MADE3 builds on the predecessor aerosol submodels MADE and MADE-in. Its main new features are the explicit representation of coarse particle interactions both with other particles and with condensable gases, and the inclusion of hydrochloric acid (HCl)chloride (Cl) partitioning between the gas and condensed phases. The aerosol size distribution is represented in the new submodel as a superposition of nine lognormal modes: one for fully soluble particles, one for insoluble particles, and one for mixed particles in each of three size ranges (Aitken, accumulation, and coarse mode size ranges). In order to assess the performance of MADE3 we compare it to its predecessor MADE and to the much more detailed particle-resolved aerosol model PartMC-MOSAIC in a box model simulation of an idealized marine boundary layer test case. MADE3 and MADE results are very similar, except in the coarse mode, where the aerosol is dominated by sea spray particles. Cl is reduced in MADE3 with respect to MADE due to the HClCl partitioning that leads to Cl removal from the sea spray aerosol in our test case. Additionally, aerosol nitrate concentration is higher in MADE3 due to the condensation of nitric acid on coarse particles. MADE3 and PartMC- MOSAIC show substantial differences in the fine particle size distributions (sizes about 2 micrometers) that could be relevant when simulating climate effects on a global scale. Nevertheless, the agreement between MADE3 and PartMC-MOSAIC is very good when it comes to coarse particle size distribution, and also in terms of aerosol composition. Considering these results and the well-established ability of MADE in reproducing observed aerosol loadings and composition, MADE3 seems suitable for application within a global model.

Mixing state↗

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↗

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↗

Conversion and Extraction of Insoluble Organic Materials in Meteorites

We endeavor to develop and implement methods in our laboratory to convert and extract insoluble organic materials (IOM) from low car-bon bearing meteorites (such as ordinary chondrites) and Precambrian terrestrial rocks for the purpose of determining IOM structure and prebiotic chemistries preserved in these types of samples. The general scheme of converting and extracting IOM in samples is summarized in Figure 1. First, powdered samples are solvent extracted in a micro-Soxhlet apparatus multiple times using solvents ranging from non-polar to polar (hexane - non-polar, dichloromethane - non-polar to polar, methanol - polar protic, and acetonitrile - polar aprotic). Second, solid residue from solvent extractions is processed using strong acids, hydrochloric and hydrofluoric, to dissolve minerals and isolate IOM. Third, the isolated IOM is subjected to both thermal (pyrolysis) and chemical (oxidation) degradation to release compounds from the macromolecular material. Finally, products from oxidation and pyrolysis are analyzed by gas chromatography - mass spectrometry (GCMS). We are working toward an integrated method and analysis scheme that will allow us to determine prebiotic chemistries in ordinary chondrites and Precambrian terrestrial rocks. Powerful techniques that we are including are stepwise, flash, and gradual pyrolysis and ruthenium tetroxide oxidation. More details of the integrated scheme will be presented.

Locke, Darren R.↗