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At least 19 records

Tests of Zinc Rich Anticorrosion Coatings

Condition of zinc-rich anticorrosion coatings after 10 years of exposure discussed in status report, which follows up on 18-month study of anticorrosion coatings on steel started in 1971. Test panels with various coatings mounted on racks on beach and checked periodically. Of panels with inorganic zinc-rich coatings, only one slightly rusted. Panels were in such good condition they were returned to beach for more exposure.

Morrison, J. D.↗

Anticorrosive epoxy coatings from direct epoxidation of bioethanol fractionated lignin

The development of lignin-based anticorrosive epoxy coatings for steel protection is beneficial for both alleviating the fossil resource depletion and value-added utilization of lignin but remains a challenge due to the inherent heterogeneous structure of lignin. Here, in this study, we selectively extract the low molecular weight (MW) fraction of a crop residue-derived enzymatic hydrolysis lignin (EHL) through a bioethanol fractionation process and prepare epoxy resin by direct epoxidation of the bioethanol fractionated lignin (BFL). The coatings are then fabricated using 20–100 wt% of BFL-based epoxy resin (LEp) as the commercial epoxy resin substitute. The low MW and high p-hydroxyphenyl content of the BFL offer high solubility and good workability for BFL and LEp during epoxidation and coating production, respectively. Lignin-based coatings with 20–40 wt% LEp exhibit good adhesion property (5B) and superior corrosion resistance, compared to the commercial epoxy coating. Although coating with high LEp concentrations (i.e., 60–100 wt%) resulted in decreased adhesion strength, the coating with 100 wt% LEp still displayed corrosion protection performance comparable to that of the commercial epoxy coating. Overall, this study provides a simple and effective approach to converting lignin to epoxy resins for a wide variety of surface coating applications.

09 BIOMASS FUELS↗

Anticorrosion studies

The aging behavior of chemically bonded interfaces between metals and pottants, such as ethylene vinyl acetate (EVA) was studied using the Dow Corning primer systems. It was observed that the primers seem to function as anticorrosive agents on metal surfaces. It was demonstrated that EVA, and the A-11861 EVA/glass primer stops corrosion of the aluminum used on the back surfaces of crystalline silicon solar cells. However, this same treatment does not work for the aluminum on the back surfaces of amorphous silicon solar cells.

Boerio, J.↗

Cross-linkable nanocomposite anticorrosion coating

Nanocomposite anticorrosion coating can be achieved by depositing alternating, multilayers of a cross-linkable polymer and dispersed and aligned inorganic platelets followed by cross-linking of the cross-linkable polymer. The cross-linkable polymer can be an externally cross-linkable polymer that is cross-linked by diffusing a cross-linking agent into the deposited multilayer coating. Alternately, the cross-linkable polymer can be a functionalized cross-linkable polymer that is cross-linked by self-curing, thermal heat curing, or light (e.g., UV) following deposition of the multilayer coating.

Percival, Stephen John↗

New Anti-Corrosive Coatings with Resin-Bonded Polyaniline and Related Electroactive Groups

It is already known that polyaniline (an electroactive polymer) functions as a corrosion inhibitor for steel and in view of the fact that it is known to perform in the presence of hydrochloric acid, it has been considered likely that it may be useful to NASA for protecting launch structures at KSC which are exposed to not only continual ocean-side salt spray but also to hydrochloric acid at the times that solid-fuel boosters are fired. The currently used zinc-rich silicate-bonded coating is not wholly protective against the hydrochloric acid. Water pollution from zinc salts is another concern. Other earlier and concurrent NASA sponsored projects have been focussed on polyaniline specifically. Our project, administered for NASA by Dr. K. Thompson of KSC and these more-specifically polyaniline-related projects are included in a CRADA coordinated by Dr. F. Via of Akzo Nobel. A parallel project at Polytechnic under Prof K. Levon concentrated more specifically on polyaniline with various dopants. Our exploratory project reported herein was aimed at broadening the range of such corrosion inhibitors, to give protective paint compounders a wider latitude for adding corrosion inhibitors having polyaniline-like performance, and thus we diverged in several probing directions from polyaniline. Our working hypothesis was that physical variants of polyaniline, such as supported formulations on pigments or carriers, and chemical variants of polyaniline, including those having no electroconductive character, may have enhanced anticorrosion activity. We also hypothesized that small (non-polymeric) molecules having structures related to those occurring in polyaniline, may be active as corrosion inhibitors. We did preliminary testing, using an ASTM salt spray method at a nearby commercial paint testing laboratory. Our most interesting findings were that a non-electroconductive meta-isomer of polyaniline showed some corrosion activity, suggesting that the features of the polyaniline molecule associated with conductivity are not necessary for the anticorrosion action. Also, signtficantly, small molecular weight aromatic diamines and diimines resembling the reduced and the oxidized repeating unit in polyaniline showed an interesting degree of anticorrosive activity, suggesting that the polymeric feature of polyaniline is not necessary for anticorrosion action.

Weil, Edward D.↗

Distinct Mechanism of Anti-Corrosion and Swelling-Adhesion Modeling of Low-Dimensional Nylon-Fluoropolymer Composite Coatings

Compared to other polymers, composite coatings with fluoropolymers as the matrix have attracted considerable interest due to their mechanical performance, chemical stability, and low surface energy. Herein, we present an anticorrosion mechanism of fluoropolymer composite coatings achieved by dispersing varying amounts of polyamide 12 (PA-12) particles over a poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) matrix. The choice of PVDF-HFP as a coating matrix was driven by its superior processability and mechanical properties over Teflon, while PA-12 afforded swelling capacity, preventing electrolyte permeation, and inhibiting matrix stress crack propagation. The corrosion resistance of the coatings was assessed mainly by potentiodynamic polarization and impedance measurements while being immersed in a NaCl solution. Our electrochemical measurement findings showed that 0.75% w/w PA-12 in the PVDF-HFP matrix significantly enhanced corrosion protection even after 21 days of immersion. Microscopy, dielectric spectroscopy, surface analysis, and mechanical testing (American Society for Testing and Materials standards) corroborated the results. PVDF-HFP coatings containing a minimum percolation threshold of 0.75 wt % PA-12 with 1 mil thickness on mild steel exhibited a remarkable increase in resistance and film adhesion, and a notable corrosion rate decrease. Finite element analysis simulation with a bilinear traction-separation law confirmed the swelling mechanism and adhesion behavior. Finally, this study highlights the potential of nylon particle dispersion in PVDF-HFP matrices as a practical approach to developing advanced anticorrosion coatings with promising practical applications in various industries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrochemical Impedance Of Inorganic-Zinc-Coated Steel

Report describes preliminary experiments to evaluate both direct-current and alternating-current electrochemical impedance measurements as candidate techniques for use in accelerated corrosion testing of mild-steel panels coated with inorganic zinc-rich primers and exposed to seaside air. Basic idea behind experiments to compare electrochemical impedance measurements with anticorrosion performances of coating materials to determine whether measurements can be used to predict performances. Part of continuing program to identify anticorrosion coating materials protecting steel panels adequately for as long as 5 years and beyond.

Macdowell, Louis G.↗

The Effect of Annealing Time on Microstructure and AC Corrosion Behavior of X80 Steel in Simulated Solution of Alkaline Soil

The alternating current (AC) corrosion behavior of X80 steels annealed for different times was investigated in an alkaline soil simulation solution by electrochemical measurement, immersion test and surface analysis technology. The results show that with or without AC interference, the steels annealed for various times have different corrosion resistance. The anticorrosion resistance of steel improves with an increase in annealing time. AC interference results in the evolution of the main cathodic reaction, and facilitates the corrosion of the steels. The steel annealed for 20 min presents a more severe corrosion degree with distinct pits. The corrosion behavior of the steels annealed for different times with AC application is closely related to the microstructure. A decrease in pearlite reduces the number of galvanic corrosion cells, decreasing the corrosion rate of steel. And the grain increase is beneficial for improving the corrosion resistance of the annealed steel.

36 MATERIALS SCIENCE↗

Corrosion resistant hot melt adhesive to bind metals

Hot melt adhesives (HMAs) play an important role in many industries, and their demand is expected to grow. HMAs don't require any solvents, and their application results in the formation of strong bonds with the substrate upon cooling within seconds. These properties differentiate them from liquid glues and make them preferable for practical application. Currently, commercial HMAs are used in bonding lightweight materials such as paper, polymers, and cartons, and have limited usage in areas necessitating the bonding of heavier objects like metals. Here, in this study, we report a design and testing of versatile platform comprising an ion-coordinating polymer and ionic fillers for performance optimization and understanding of structure–property relationships, enabling the rational design of HMAs with improved adhesion to metal surfaces. All-atom Molecular dynamics (MD) simulations and various characterization methods are used to elucidate the adhesion mechanism in model composite system containing polyethylene oxide mixed with chemically diverse salt particles. The maximum adhesion strength is found in composites with Al(OH) 3 and FeCl 3 fillers. Interestingly, the presence of Al(OH) 3 also provides a multifunctional anticorrosion property as measured electrochemically using the Tafel method. The discovered path to formulations with improved adhesion to metal surfaces constitutes an important step toward advancing HMAs for use in the structural and semi-structural metal work domain.

Adhesive and cohesive forces↗

Evaluation of thermal energy storage for central receiver concentrating solar power plants under charging cycles through structural assessment

Electricity production by concentrated solar power (CSP) systems has stood out among energy transition alternatives due to their large generation capacity (between 30 MW and 400 MW) and high capacity factor (80%) when incorporating thermal storage systems (TES). Although TES tanks in operation worldwide are made of austenitic steels with remarkable mechanical and anticorrosive properties, operational failures have been reported due to low-cycle fatigue, creep, and the abrupt release of residual stresses generated during tank manufacturing. A critical operation for salt tanks is the initial daily charging operation, given the low fluid level and the thermal gradients between the inventory and the salt entering the tank. This study presents a structural simulation of a 39.6 m-diameter molten salt tank for central receiver CSP plants, accounting for temperature and pressure variations during charging and different sparger ring inlet configurations. The initial pre-stressed condition of the floor, resulting from the manufacture of welded plates, is used as a boundary condition. The fatigue and creep life analyses were performed in accordance with the ASME BPVC and API standards. It was found that the tank's floor is in a less favourable mechanical condition than the wall, due to its initial manufacturing condition and the maximum temperature differences during charging. A critical zone was identified in an area affected by residual stress on the floor and under the sparger ring. The baseline sparger ring configuration, with 52 2-inch-diameter orifices and a flow direction of 90 degrees , results in an average floor stress of approximately 25 MPa and creep damage after 1.2 years of tank operation.

14 SOLAR ENERGY↗

Research on oxygen solubility in aqueous amine solvents with common additives used for CO 2 chemical absorption

Oxidative degradation in amine based post-combustion carbon capture (PCCC) leads to solvent losses and decreased solvent performance. Oxygen (O 2 ) in the flue gas is dissolved into the aqueous solvent and can reactively degrade the amine component. Advanced aqueous amine solvents are designed to contain additional surfactant and anti-foam additives as well as two types of corrosion inhibitors. These additives contribute to improve the solvent performance while reducing foaming and corrosion of expensive equipment. This work examines the impact of these additives on oxygen solubility (or dissolved oxygen - DO) in various aqueous amines used in PCCC including ethanolamine (MEA), 1-amino-2-propanol (A2P), 2-amino-1-propanol (2A1P), 2-(methylamino)-ethanol (NMEA), 2-(ethylamine)-ethanol (2EAE), diethanolamine (DEA), methyl-diethanolamine (MDEA), dimethylethanolamine (DMEA), piperazine (PZ), 1,2-ethyldiamine (EDA), and 1,6 hexadiamine (HDA). Further, the impact of carbon loading on oxygen solubility with and without these additives was also examined. The surfactant and anti-foam additives had minimal impact on DO for all the solvents investigated. The two anticorrosion additives had opposite effects in the measured DO, 2- mercaptobenzothiazole (MBT) decreased the DO concentration, and sodium metavanadate showed an increase. These results indicate that several of these common additives can be expected to minimally affect DO related oxidative degradation in these advance amine solvents.

60 APPLIED LIFE SCIENCES↗

Reductive removal of pertechnetate and chromate by zero valent iron under variable ionic strength conditions

Radioactive technetium-99 (Tc) present in waste streams and subsurface plumes at legacy nuclear reprocessing sites worldwide poses potential risks to human health and the environment. This research comparatively evaluated efficiency of zero valent iron (ZVI) toward reductive removal of Tc(VII) in presence of Cr(VI) from NaCl and Na 2 SO 4 electrolyte solutions under aerobic conditions. In both electrolytes, anticorrosive Cr(VI) suppressed oxidation of ZVI at elevated concentrations resulting in the delay of initiation of Tc(VII) reduction to Tc(IV)). In the absence of Cr(VI), no such delay was observed in the analogous systems. At low ionic strength, retarded ZVI oxidation inhibited Tc(VII) reduction in part due to the competing thermodynamically more favorable reduction of Cr(VI) to Cr(III); this effect was particularly pronounced in the chloride medium at the ionic strength ? 0.1. Higher ionic strength favored reduction of both Tc(VII) and Cr(VI), which followed a second-order reaction rate in both electrolytes attributed to the more efficient iron oxidation as evident from x-ray diffraction and electron microscopy measurements. Magnetite was the primary iron oxide phase, and its higher fraction in the SO 4 2- solutions facilitated reductive removal of Tc(VII) and Cr(VI). In the Cl- matrix, Cr(VI) promoted further oxidation of magnetite as well as formation of chromite diminishing overall reductive capacity of this system and resulting in less effective removal of Tc(VII) compared to the SO 4 2- solutions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

In Situ Oxidation Studies of High-Entropy Alloy Nanoparticles

Although high-entropy alloys (HEAs) have shown tremendous potential for elevated temperature, anticorrosion, and catalysis applications, little is known on how HEA materials behave under complex service environments. Herein, we studied the high-temperature oxidation behavior of Fe 0.28 Co 0.21 Ni 0.20 Cu 0.08 Pt 0.23 HEA nanoparticles (NPs) in an atmospheric pressure dry air environment by in situ gas-cell transmission electron microscopy. It is found that the oxidation of HEA NPs is governed by Kirkendall effects with logarithmic oxidation rates rather than parabolic as predicted by Wagner's theory. Further, the HEA NPs are found to oxidize at a significantly slower rate compared to monometallic NPs. The outward diffusion of transition metals and formation of disordered oxide layer are observed in real time and confirmed through analytical energy dispersive spectroscopy, and electron energy loss spectroscopy characterizations. Localized ordered lattices are identified in the oxide, suggesting the formation of Fe 2 O 3 , CoO, NiO, and CuO crystallites in an overall disordered matrix. Hybrid Monte Carlo and molecular dynamics simulations based on first-principles energies and forces support these findings and show that the oxidation drives surface segregation of Fe, Co, Ni, and Cu, while Pt stays in the core region. The present work offers key insights into how HEA NPs behave under high-temperature oxidizing environment and sheds light on future design of highly stable alloys under complex service conditions.

36 MATERIALS SCIENCE↗

Electrochemical Synthesis of Zeolite Coatings with Controlled Crystal Polymorphism and Self-Regulating Growth

Zeolite coatings are studied as molecular sieves for membrane separation, membrane reactors, and chemical sensor applications. They are also studied as anticorrosive films for metals and alloys, antimicrobial and hydrophobic films for heating, ventilation, and air conditioning, and dielectrics for semiconductor applications. Zeolite coatings are synthesized by hydrothermal, ionothermal, and dry-gel conversion approaches, which require high process temperatures and lengthy times (ranging from hours to days). Here, we report the first zeolite coatings synthesized via electrochemical deposition on a cathodic electrode, with controlled crystal polymorphism achieved within subhourly duration. We demonstrate this approach by developing sodium zeolite (e.g., sodalite (SOD), NaA (LTA), and Linde Type N (LTN)) coatings on a titanium electrode and extending the synthesis method to porous stainless steel. The coating morphology and crystallinity depend on the temperature, time, and applied current. The coating thickness is independent of the applied current, showing the presence of a self-regulating mechanism to ensure a uniform coating thickness across the metal surface. The electrochemical zeolite growth mechanism was elucidated with high-resolution transmission electron microscopy, and applications of the resultant zeolite coatings for oil/water separation and ethanol/water pervaporation were exploited. Electrochemical synthesis represents a novel, simple, fast, and environmentally friendly approach to preparing zeolite coatings. It can potentially be generalized for developing zeolite materials with diverse framework structures, morphologies, and orientations for substrates with complicated geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Laboratory-Scale Coal-Derived Graphene Process (Final Report)

The Energy & Environmental Research Center (EERC) conducted a laboratory-scale coal-derived graphene (CDG) project focused on developing a technological process for making graphene from four U.S. domestic coal or coal wastes, including lignite from North Dakota, subbituminous coal from Wyoming, bituminous coal from Utah, and anthracite from Pennsylvania. The project was divided into two performance or budget periods (BPs), with BP1 comprising the up-front laboratory experiments to make graphene materials from coal beginning on May 1, 2020, to April 30, 2022. BP2 was conducted from May 1, 2022, to April 30, 2023, and was focused on analyzing the CDG process economic feasibility and the technical gaps for technological scale-up and commercialization. During this project, a few different coal-derived high-value products have been demonstrated, including graphite, graphene oxide (GO), reduced graphene oxide (rGO), and graphene quantum dots (GQDs). A new graphite microstructure was discovered and named “croissant graphite” because of the exterior morphological and textural resemblance to croissant food items sold in commercial groceries stores. The new graphite structure and the associated preparation from coal or coal waste feedstocks has been the subject of a U.S. patent application. The systematic experimental processes involving coal cleaning, upgrading, and conversion to high-value carbon products culminated into a developed upgraded coal-to-products (UCP) technology that is being pursued for potential fast-track commercialization, if funding is available. It is envisioned that commercialization of the UCP technology would increase consumption of U.S. domestic coals or coal wastes to make environmentally sustainable high-value products for the electronics industry, high-energy-storage applications, and clean energy technologies such as electric vehicle (EV) lithium-ion batteries (LIBs), for which graphite has become a critical mineral commodity. Croissant graphite microstructures, when observed by field emission scanning electron microscopy (FESEM), display wavy surface morphology and often grow from a base that is made of graphitized particles with honeycomb-like layers, which are believed to be graphene layers. While more studies are needed to fully ascertain the mechanisms of the croissant graphite microstructure formation, it is postulated that their growth may begin from curling of the graphene sheets into ribbon-like structures, and continuous growth and densification of the ribbon-like structures forms croissant microstructures. Additional studies are ongoing to evaluate the electrochemical performance of croissant graphite for LIB applications and to determine the experimental conditions necessary to tune on/off croissant formation so that it can be either optimized or suppressed depending on performance evaluation results. In addition to the discovery of croissant graphite, the graphitization process from the four coal ranks in general was successful. X-ray diffraction (XRD) analysis showed that the degree of graphitization (DoG) ranged from 12% to 80% in an early sample set, and further optimization on lignite coal produces a DoG of about 92%, which was spectacular to see as lignite is the lowest-rank coal. Thus, it is expected that the graphitization performance for higher-rank coals will be similar or better when optimized as well. The coal-derived graphite was used to make GO and rGO. Analytical characterization, e.g., by methods such as Raman spectroscopy, XRD, Fourier transform infrared (FTIR) spectroscopy and FESEM, showed that the sequence of converting the coal to graphite, exfoliating it to GO, and then chemically reducing the GO to rGO was successful. Although coal naturally contains aromatic compounds and some relatively small-sized condensed aromatic units, it does not contain graphene sheets. In the UCP process, the aromatic domains in the coals, particularly low-rank coals, are concentrated and condensed further into graphene sheets, which are ordered into a 3D stack during graphitization. The synthesized graphite is then unpacked by methods such as exfoliation to various graphene products. GQDs were synthesized from all four coal types, and their optical properties were demonstrated to be tunable by the coal precursor preprocessing treatments. In all four coal types, enhanced optical properties were observed for the produced GDQs with incremental improvements made to the coal precursors. GQDs produced from raw coal samples displayed lower ultraviolet–visible (UV–Vis) spectroscopy absorbance intensity compared to those obtained from cleaned and upgraded coal residues. The photoluminescence (PL) intensities also varied with pretreatment conditions and with the concentration of GQDs in aqueous solutions. GQDs obtained from anthracite show longer emission wavelengths and can be excited by visible light as opposed to GQDs derived from the other coal ranks. UV fluorescence 3D maps and spectra revealed that the emission wavelength at which the GQDs solutions display the highest intensity was slightly redshifted based on the coal precursor pretreatments. In low-rank coal (lignite and subbituminous) samples, two clusters were observed in the maps for GQDs, which may suggest that there are potentially two types of fluorophores in solution or two main size populations. The ability to tune the properties of GQDs based on processing methods can be exploited to make GQDs for various optical display or optoelectronics applications. The results also highlight the importance of removing coal-borne impurities to improve the quality of the coal precursor for preparation of graphene products. Coal and/or coal wastes preprocessing methods were developed and applied to clean and upgrade the coal precursors prior to graphitization and subsequent conversion to graphene products. The preprocessing methods involve high specific-gravity separations, mineral acid cleaning (no hydrofluoric acid), and subsequent upgrading by reducing the coal-borne heteroatom (nitrogen, sulfur, and oxygen) content using proprietary chemical agents. Analytical characterization revealed that the preprocessing steps were successful, with ash reductions that range from 38% to 80% and residual ash content that was below the 5 wt% initial target. Based on proximate and ultimate analysis, the heteroatom reduction reactions produced upgraded coal residues with the oxygen content reduced by 8% to 24%, with additional reductions in the nitrogen and sulfur contents. An initial assessment of the waste streams from the UCP process shows very small to negligible environmental impact due to CO 2 , NO x , and SO x because most process steps are performed under inert atmosphere with argon. Consequently, reactive oxygen environments that tend to create these species are avoided. The inorganic and potentially hazardous species are released into aqueous waste streams that are easy to handle for proper disposal. The liquid waste streams were found to contain low-level concentrations of rare-earth elements (REEs), which could be concentrated and recovered as value-added by-products. Additionally, the volatile and gaseous fractions from carbonization and heat treatment contain useful organic compounds that can also be recovered as potential valuable by-products. Thus, the UCP technology is considered an environmentally sustainable and promising emerging technology for making high-value products from coal and coal wastes, with potential additional value-added by-products. Analysis of potential markets for the coal-derived carbon products shows a strong demand in both niche market sectors and across a wide variety of other industrial sectors. Graphite is currently considered a critical mineral commodity that has a large and growing demand in the LIB industry for EV applications. Based on data from Fortune Business Insights (2022) and Marketwatch (2023) reports, the average global graphite market is projected to reach about 33 billion by 2028, growing at a compound annual growth rate (CAGR) of about 7%, with much of this growth expected to be in the LIB industry. GO and rGO have strong market potentials in various application areas, such as coatings for anticorrosion, anti-icing, and antimicrobial protection, thermal barriers, wear resistance, sensors, additive manufacturing such as 3D inks, and others. GQDs are the emerging key player in the bioimaging, photovoltaics, and light-emitting diodes (LEDs) applications, with the potential to replace traditional semiconductor quantum dots (SQDs), which are based on metallic systems that are more toxic and more expensive. Biomedical applications of GQDs are becoming more attractive because of low to no toxicity and extremely low cost compared to SQDs. The major challenges for scale-up and commercialization of coal-derived carbon products such as graphene vary from the inherent attributes of graphene itself to reluctance to accept graphene in new manufacturing processes because of the uncertainty of the unknown. The 2D nature of graphene materials with a thickness of one atom presents significant challenges to proper handling/processing, and process scale-up becomes difficult because it requires high-end, expensive equipment, even for routine handling and analysis for quality assurance and control. Pristine graphene can also be extremely difficult to work into other matrices, thus hindering downstream processibility, especially at large scale. Currently, the cost of graphene and graphene products is still high and presents an economic risk that tends to slow down investment in scaling up emerging technologies. The lack of a standard for graphene materials for quality assurance and quality control poses a great challenge not only for the markets but also for commercialization efforts. A first-look economic feasibility analysis of the UCP technology provided valuable information that suggests the UCP process would be feasible, especially when it is scaled to a pilot scale and could be more competitive at the full scale. Graphitization was found to be the most energy-consuming and most capital-intensive step in the overall process. In small laboratory- and bench-scale experiments, labor is a significant contributor to the total process costs. Although these energy, capital, and labor constraints contribute to a higher selling price for the product, a preliminary economic model suggests that the process would be feasible at large scale when the process is fully integrated, optimized, and automated.

01 COAL, LIGNITE, AND PEAT↗

Thermal oxidative degradation reactions of perfluoroalkylethers

The mechanisms operative in thermal oxidative degradation of Fomblin Z and hexafluoropropene oxide derived fluids and the effect of alloys and additives upon these processes are investigated. The nature of arrangements responsible for the inherent thermal oxidative instability of the Fomblin Z fluids is not established. It was determined that this behavior is not associated with hydrogen end groups or peroxy linkages. The degradation rate of these fluids at elevated temperatures in oxidizing atmospheres is dependent on the surface/volume ratio. Once a limiting ratio is reached, a steady rate appears to be attained. Based on elemental analysis and oxygen consumption data, CF2OCF2CF2O2, no. CF2CF2O, is one of the major arrangements present. The action of the M-50 and Ti(4 Al, 4 Mn) alloys is much more drastic in the case of Fomblin Z fluids than that observed for the hexafluoropropene derived materials. The effectiveness of antioxidation anticorrosion additives, P-3 and phospha-s-triazine, in the presence of metal alloys is very limited at 316 C; at 288 C the additives arrested almost completely the fluid degradation. The phospha-s-triazine appears to be at least twice as effective as the P-3 compound; it also protected the coupon better. The Ti(4 Al, 4 Mn) alloy degraded the fluid mainly by chain scission processes this takes place to a much lesser degree with M-50.

Paciorek, K. L.↗

Stabilizing PFAE Against Oxidation

Process makes commercial perfluoroalkylether (PFAE) hydraulic fluid more stable in presence of metals in hot oxidizing atmospheres. Consists of thermal oxidation in presence of catalyst to remove weak links, followed by transformation of newly-created functional groups into phospha-s-triazine linkages, which impart antioxidation and anticorrosion properties. A 66-percent yield of stable PFAE obtained. Fluid used as lubricant, grease, or hydraulic fluid at temperatures from -55 to +300 degree C in presence of metals in oxidizing atmosphere.

Jones, W. R., Jr.↗

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↗