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At least 433 records · Page 24

Quantifying Properties for a Mechanistic, Predictive Understanding of Aqueous Impact on Aging of Medium and Low Voltage AC and DC Cabling in Nuclear Power Plants

To address the gap in knowledge in understanding degradation in relevant service conditions, this project aimed to develop a mechanistic, predictive model of medium and low voltage cable failure based on the primary environmental degradation parameters of aqueous immersion time, temperature, and the oxidation extent. To do so, we took a two-fold approach toward evaluating degradation as related to the aqueous condition. First, we evaluated the chemical, mechanical, and electrical properties of polymers that comprise the cabling insulation under varied aqueous conditions at different temperatures. Secondly, we evaluated the performance of insulation materials under similar accelerated aging conditions in addition to the dielectric breakdown of the cabling under submersion conditions. Thermal oxidation and immersion of LDPE thin films were done using a Parr vessel and the extent of oxidation was monitored using the carbonyl index from ATR-FTIR spectrum, a ratio quantifying the carbonyl functionality produced on the LDPE film surface. Increasing the temperature, oxidation time, and oxygen pressure increased the water-vapor permeability and the carbonyl content. Thermogravimetric analysis of the films confirmed that there is indeed an initial weight loss of the smaller molecular weight molecules and volatiles. At higher temperatures, there is a secondary mass loss. Up to 70°C, the mass loss curves were similar until 80°C, when the aged films decreased at a much greater rate with respect to increasing temperature. This was seen in the 10, 50, 90% weight loss temperatures. The mechanical properties of sheet PP and HDPE as well as injection molded LDPE, HDPE, HDPP dog bones were plotted with respect to the time spent in the Parr vessel during thermal oxidation. For the sheet PP and HDPE, the UTS and the modulus of elasticity decreased while the elongation increased. The injection-molded LDPE, HDPE, and HDPP dog bones experienced a similar trend where the changes in the properties were within experimental uncertainty. This analysis of LDPE in dry and immersive oxygen-rich environments is an important baseline for future experiments looking at other degradation mechanisms. A predictive aging model for low-density polyethylene insulative cable housings was developed. This model revealed a combination of physical and chemical processes which lead to an increase in permeability and a decrease in strength of the insulator. In creating this predictive model, a gap of knowledge in the literature was revealed in two areas: understanding how the crystallinity of a polymer changes with time and visualizing the predicted pores formed through the insulator which leads to failure. Developing and using an adapted ATR-FTIR method, crystallinity was monitored and compared to bulk crystallinity found via DSC. Inhomogeneity in crystallinity changes were observed but the FTIR method but was found to be less reliable. Pore visualization was found utilizing electrical impedance spectroscopy saturated aged polyethylene films with synthesized citrate-capped gold nanoparticles, and chloroauric acid precursor. results indicate a decreasing impedance of the polyethylene films caused by the transport of ions through the film. SEM imaging was then performed for elemental analysis of the films and counter electrodes for the presence of ions. Chloride and gold ions were detected; however, no nanoparticles were found. This gives an estimated pore size of at least 0.3 nm through the aged film. Cyclic submergence of polyethylene and polypropylene in aqueous solutions of copper sulfate and Harrison’s solution were examined. It was discovered that aging in these mixed conditions and at 90°C did cause a small, yet significant increase to tensile strength for both unaged polyethylene and polypropylene. The PE and PP in cycled and submerged conditions did not have tensile strengths significantly different from dry-aged after 16 weeks. For both solutions, it was determined that capacitance increases with both water tree depth and cable temperature and is relatively independent of changing water tree AR. As for resistance, there is no apparent change between depth percentages of 10 and 80 for both solutions. This is because the water tree has not yet entered the conductor and thus there is no shorting current flowing through the tree yet. Between 80 and 100% water tree depth, it is observed that for both solutions there is a rapid decrease in resistance because the tree is now impacting the conductor shield and allowing shorting current to flow through it. The relationship between resistance and temperature was found to be inversed. As temperature increases, resistance decreases for both water tree solutions with distilled water having the most apparent difference across the range of temperatures simulated. With regards to water tree AR, resistance was found to be relatively independent at depth percentages of 10, 50, and 70, but there was some relationship at 100% depth for both solutions. At this depth, as water tree AR increased, resistance was found to also increase. Through the examination of voltage and electric field distribution plots, it was confirmed for EPR cables that increasing water tree depth leads to increasing distortion. The increase in shorting current at 100% depth for aqueous copper sulfate compared to distilled water was also visualized. Lastly, the relationship between shorting current and temperature for narrow water trees was visualized and validated using the distribution plots. This study has led to a better understanding of the effect of cable temperature, water tree solution, and geometry of the tree region on cable degradation. Furthermore, this study has documented simulation results of water tree degradation in EPR MV cables, which had been previously lacking in information. Future work in this area will add frequency into the mix and examine what effect it has on the rate of cable degradation as a result of water treeing. To compliment the work being carried by UMD on different polymer chemistries, harvested medium voltage (MV) cables were selected for accelerated aging study at ORNL. These medium voltage cables are representative of the vintages and materials that are currently in use at existing nuclear power plants (NPPs). These cables were immersed in water at 90°C and energized for a period of two years at elevated voltage. Partial discharge was measured during this period of time to track potential degradation. Unfortunately, due to the absence of failure, the extent of integration between the UMD techniques and the harvested MV insulation was limited. However, based on the findings and from the UMD research in the previous sections on polyethylene and polypropylene, follow-on characterization for harvested MV cable insulation should focus on sample preparation to take advantage of the UMD techniques to better understand mechanistic degradation in MV cable insulations. This would include: 1.) Utilization of solutions and impedance measurement insulation to track permeability in harvested and accelerated aging insulation samples, 2.) Adaptation of gold nanoparticle synthesis for electrical impedance spectroscopy with supporting SEM characterization to study pore formation in harvested and accelerated aged insulation samples, & 3.) ATR-FTIR crystallinity with multiple temperature dependent harvested MV cable insulation under different air and submerged accelerated aging. In addition, low voltage dielectric spectroscopy and high voltage dissipation factor, tan δ, could be implemented as a condition monitoring tool for harvested MV cable insulation in submerged environments.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Durability of Environmental Barrier Coatings in a Water Vapor/Oxygen Environment

Silicon carbide (Sic) and silicon nitride (Si3N4) show potential for application in the hot sections of advanced jet engines. The oxidation behavior of these materials has been studied in great detail. In a pure oxygen environment, a silica (SiO2) layer forms on the surface and provides protection from further oxidation. Initial oxidation is rapid, but slows as silica layer grows; this is known as parabolic oxidation. When exposed to model fuel-lean combustion applications (standard in jet engines), wherein the partial pressure of water vapor is approximately 0.5 atm., these materials exhibit different characteristics. In such an environment, the primary oxidant to form silica is water vapor. At the same time, water vapor reacts with the surface oxide to form gaseous silicon hydroxide (Si(OH)4). The simultaneous formation of both silica and Si(OH)4 -the latter which is lost to the atmosphere- the material continues to recede. Recession rates for uncoated Sic and Si3N4 are unacceptably high, for use in jet engines, - on the order of 1mm/4000h. External coatings have been developed that protect Si-based materials from water vapor attack. One such coating consists of a Ba(0.75)Sr(0.25)Al2Si2O8 (BSAS) topcoat, a mullite/BSAS intermediate layer and a Si bond coat. The key function of the topcoat is to protect the Si-base material from water vapor; therefore it must be fairly stable in water vapor (recession rate of about 1mm/40,000h) and remain crack free. Although BSAS is much more resistant to water vapor attack than pure silica, it exhibits a linear weight loss in 50% H2O - 50% O2 at 1500 C. The objective of my research is to determine the oxidation behavior of a number of alternate hot-pressed monolithic top coat candidates. Potential coatings were exposed at 1500 C to a 50% H2O - 50% O2 gas mixture flowing at 4.4 cm/s . These included rare- earth silicates, barium-strontium aluminosilicates. When weight changes were measured with a continuously recording microbalance, linear weight loss was observed. BSAS materials have a fairly high volatility at this temperature, but rare-earth mono-silicate compounds were significantly more stable.

Holchin, John E.↗

The effects of atomic oxygen on polymeric materials

At the altitudes of low-earth orbit (LEO), atomic oxygen (AO) is the most abundant chemical species. This strong oxidizing agent reacts with virtually any organic material that is not already fully oxidized. Erosion by AO can be extensive and jeopardizes any protective coatings, thermal blankets, adhesives, and structural composites exposed on the exterior of satellites in LEO. Researchers prepared and tested organic materials for their susceptibility to AO using a commercial plasma asher which approximately simulates the oxygen effects in LEO. Experiments were performed on a polyimide, a polysulfone, and two epoxy adhesives into which low molecular-weight additives have been dissolved. Incorporated in the molecular structure of these additives are elements such as silicon whose nonvolatile oxides, which are formed on exposure to AO, remain as a coating on the surface to create a barrier between the remainder of the organic material and the AO. We find that the additives protect the materials, but the low solubility of some limit their utility. Concurrent studies are underway to measure the effect of the additives on the thermal expansion coefficients of the materials. Tows of aramid fibers, which are important components in the proposed tether satellite systems, have been eroded in the asher. The results which show that the square root of the mass remaining decreases linearly with the time of exposure (see the figure) are consistent with a constant rate of surface erosion. The tensile strength of these eroded tows decreases with time of exposure also; additional measurements are in progress.

Orwoll, Robert A.↗

Cost-Cutting Powdered Lubricant

Scientists at NASA's Glenn Research Center developed a high-temperature, solid lubricant coating material that is saving the manufacturing industry millions of dollars. The material came out of 3 decades of tribological research, work studying high-temperature friction, lubrication, and the wearing of interacting surfaces that are in relative motion. It was developed as a shaft coating deposited by thermal spraying to protect foil air bearings used in oil-free turbomachinery, like gas turbines, and is meant to be part of a larger project: an oil-free aircraft engine capable of operating at high temperatures with increased reliability, lowered weight, reduced maintenance requirements, and increased power. This advanced coating, PS300, is a self-lubricating bearing material containing chromium oxide, with additions of a low-temperature start up lubricant (silver) and a high-temperature lubricant, making it remarkably stable at high temperatures, and better suited than previously available materials for high-stress conditions. It improves efficiency, lowers friction, reduces emissions, and has been used by NASA in advanced aeropropulsion engines, refrigeration compressors, turbochargers, and hybrid electrical turbogenerators. PS300 is ideal in any application where lowered weight and reduced maintenance are desired, and high-temperature uses and heavy operating speeds are expected. It has notable uses for the Space Agency, but it has even further-reaching potential for the industrial realm.

Source record↗

Adjusting Measured Weight Loss of Aged Graphite Fabric/PMR-15 Composites

The purposes of this study were to evaluate the growth of the surface damage layer in polymer matrix composites (PMC's) fabricated with graphite fabric reinforcement and to determine the effects of the cut-surface degradation on the overall thermo-oxidative (TOS) stability of these materials. Four important conclusions were made about the TOS behavior of T650-35/PNIR- 15 fabric-reinforced composites: (1) Three stages of composite weight loss were seen on the plot of weight loss versus aging time; (2) the depth of the cut-edge damage is related to the composite thickness; (3) the actual weight loss realized by a mechanical test specimen that has had all the aging-induced cut-edge damage removed during the preparation process is significantly less than the weight loss measured using specimens with a high percentage of cut edges exposed to the damaging environment; and (4) an extrapolation of a section of the weight loss curve can be used to obtain a more correct estimate of the actual weight loss after extended periods of aging at elevated temperatures.

Bowles, Kenneth J.↗

Oxidation Protection of Porous Reaction-Bonded Silicon Nitride

Oxidation kinetics of both as-fabricated and coated reaction-bonded silicon nitride (RBSN) were studied at 900 and 1000 C with thermogravimetry. Uncoated RBSN exhibited internal oxidation and parabolic kinetics. An amorphous Si-C-O coating provided the greatest degree of protection to oxygen, with a small linear weight loss observed. Linear weight gains were measured on samples with an amorphous Si-N-C coating. Chemically vapor deposited (CVD) Si3N4 coated RBSN exhibited parabolic kinetics, and the coating cracked severely. A continuous-SiC-fiber-reinforced RBSN composite was also coated with the Si-C-O material, but no substantial oxidation protection was observed.

Fox, D. S.↗

Titanium-Oxygen Reactivity Study

A program has been conducted at Astronautics to investigate the likelihood of occurrence of the catastrophic oxidation of titanium alloy sheet under conditions which simulate certain cases of accidental failure of the metal while it is in contact with liquid or gaseous oxygen. Three methods of fracturing the metal were used; they consisted of mechanical puncture, tensile fracture of welded joints, and perforation by very high velocity particles. The results of the tests which have been conducted provide further evidence of the reactivity of titanium with liquid and gaseous oxygen. The evidence indicates that the rapid fracturing of titanium sheet while it is in contact with oxygen initiates the catastrophic oxidation reaction. Initiation occurred when the speed of the fracture was some few feet per second, as in both the drop-weight puncture tests and the static tensile fracture tests of welded joints, as well as when the speed was several thousand feet per second, as in the simulated micrometeoroid penetration tests. The slow propagation of a crack, however, did not initiate the reaction. It may logically be concluded that the localized frictional heat of rapid fracture and/or spontaneous oxidation (exothermic) of minute particles emanating from the fracture cause initiation of the reaction. Under conditions of slow fracture, however, the small heat generated may be adequately dissipated and the reaction is not initiated. A portion of the study conducted consisted of investigating various means by which the reaction might be retarded or prevented. Providing a "barrier" at the titanium-oxygen interface consisting of either aluminum metal or a coating of a petroleum base corrosion inhibitor appeared to be only partially effective in retarding the reaction. The accidental puncturing or similar rupturing of thin-walled pressurized oxygen tanks on missiles and space vehicle will usually constitute loss of function, and may sometimes cause their catastrophic destruction by explosive decompression regardless of the type of material used for their construction. In the case of tanks constructed of titanium alloys the added risk is incurred of catastrophic burning of the tanks. In view of this it is recommended that thin-walled tanks constructed of titanium alloys should not be used to contain liquid or gaseous oxygen.

Chafey, J. E.↗

Mach 1 oxidation of thoriated nickel chromium at 1204 C /2200 F/.

Electropolished and ground samples of TD-NiCr were exposed to a 1-atm, Mach 1 gas stream at 1204 C for times up to 50 hr. The samples were subjected to both cyclic and isothermal exposure. Weight change, metal loss, X-ray diffraction, metallographic, and electron microprobe analyses were performed. Neither surface preparation nor cyclic-against-isothermal-exposure conditions had a strong effect on the oxidation behavior of the alloy. Initially, a Cr2O3 layer was formed whose volatilization resulted in a very rapid loss of metal - more than 40 microns in the first hour. At about 1 hr, the Cr2O3 layer broke down and NiO began to cover the surface. By 5 hr, the NiO had covered the surface and the rate of loss slowed. The rate-controlling step was diffusion of Cr through NiO.

Lowell, C. E.↗

Thermo-oxidative stability of graphite fiber/PMR-15 polyimide composites at 350 deg C

A series of graphite fiber/PMR-15 polyimide composites were subjected to isothermal aging at 350 C in flowing air (100 cc/min and 1000 cc/min) over a 520 hr time period. The graphite fibers were analyzed by ISS/SIMS techniques before composite fabrication. Fibers exposed at the surface of the composite due to the isothermal aging process were also analyzed by the ISS/SIMS method. Component and composite weight less studies were also conducted for similarly exposed materials. Optical micrograph investigations of composites to follow the progress of the thermo-oxidative process were also conducted. Flexural and interlaminar shear strengths of the imaged and aged composites were measured. The relationship of component and composite properties as they relate to the thermo-oxidative behavior of the materials was discussed.

Scola, D. A.↗

Hugoniot states and optical response of soda lime glass shock compressed to 120 GPa

In contrast to relatively pure silica glass (fused silica-FS), commercial silica-rich glasses contain significant fractions of additional oxide components. In particular, soda-lime glass (SLG) consists of approximately 71% SiO 2 by weight, which raises the question: what is the effect of additional cations on the shock compression response of silica-rich glasses? To address this concern, plate impact experiments were conducted to determine the high-pressure Hugoniot states for shocked SLG (37 to 120 GPa) and compared with recently reported results on FS. Using laser interferometry, particle velocity profiles were measured at the impact surface and the SLG/LiF window interface. In all experiments, the transmitted profiles show a single shock wave, with no features indicative of a phase transformation. The Hugoniot states determined from the wave profiles are described well using a linear shock velocity–particle velocity relation. Interferometry measurements (using 1550-nm wavelength laser) at the impact surface show that SLG is transparent when shocked to 55 GPa, transparent for tens of nanoseconds after impact between 55 and 81 GPa, and opaque beyond 81 GPa. From impact surface measurements, a linear relationship between the apparent and true particle velocity was observed, resulting in a linear relationship between the refractive index (at 1550 nm) and density. At 120 GPa, the SLG density is nearly twice its ambient value, indicating that SLG can achieve highly dense amorphous states. When compared to FS, shocked SLG is much less compressible and likely does not transform to a crystalline phase. A plausible explanation for this difference is indicated.

58 GEOSCIENCES↗

Novel improved PMR polyimides

The development of a class of high-temperature-resistant resins known as PMR polyimides has been reported by Serafini et al. (1972). Serafini and Vannucci (1975) found that the lower formulated molecular weight (FMW) compositions exhibited increased resin flow, but with some sacrifice in elevated temperature thermo-oxidative stability. Vannucci (1977) reported that the resin flow characteristics of the PMR composition having an FMW of 1500 could be varied by controlling the degree of resin advancement or imidization. The current investigation is concerned with an alternative approach to obtain improved flow PMR polyimides without sacrificing the desirable thermo-oxidative characteristics. The new approach is based on the utilization of a chemically compatible flow modifying agent. This agent is N-phenylnadimide (PN). The determination of the processing characteristics and properties of PN modified PMR/Celion 6000 composites is discussed.

Pater, R. H.↗

Supercritical water oxidation of products of human metabolism

Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

Tester, Jefferson W.↗

More Cyclic-Oxidation Data For Turbine Alloys

Document presents data on cyclic oxidation of high-temperature, high-strength, nickel-base and cobalt-base alloys for turbines. Completes presentation of data begun in NASA Technical Memorandum 83665 (Revised 1989), "High-Temperature Cyclic Oxidation Data, Turbine Alloys, Part 1." Data consist of plots and tabulations of changes in specific weight as function of time, and lists of surface and spalled material phases identified by x-ray diffraction measurements.

Barrett, Charles A.↗

Carbon Isotope Characterization of Organic Intermediaries in Hydrothermal Hydrocarbon Synthesis by Pyrolysis-GC-MS-C-IRMS

We report results of experiments designed to characterize the carbon isotope composition of intermediate organic compounds produced as a result of mineral surface catalyzed reactions. The impetus for this work stems from recently reported detection of methane in the Martian atmosphere coupled with evidence showing extensive water-rock interaction during Martian history. Abiotic formation by Fischer-Tropsch-type (FTT) synthesis during serpentinization reactions may be one possible process responsible for methane generation on Mars, and measurement of carbon and hydrogen isotopes of intermediary organic compounds can help constrain the origin of this methane. Of particular interest within the context of this work is the isotopic composition of organic intermediaries produced on the surfaces of mineral catalysts (i.e. magnetite) during hydrothermal experiments, and the ability to make meaningful and reproducible isotope measurements. Our isotope measurements utilize a unique analytical technique combining Pyrolysis-Gas Chromatograph-Mass Spectrometry-Combustion-Isotope Ratio Mass Specrometry (Py-GC-MS-C-IRMS). Others have conducted similar pyrolysis-IRMS experiments on low molecular weight organic acids (Dias, et al, Organic Geochemistry, 33 [2002]). Our technique differs in that it carries a split of the pyrolyzed GC-separated product to a Thermo DSQ-II quadrupole mass spectrometer as a means of making qualitative and semi-quantitative compositional measurements of the organic compounds. A sample of carboxylic acid (mixture of C1 through C6) was pyrolyzed at 100 XC and passed through the GC-MS-C-IRMS (combusted at 940 XC). In order to test the reliability of our technique we compared the _13C composition of different molecular weight organic acids (from C1 through C6) extracted individually by the traditional sealed-tube cupric oxide combustion (940 XC) method with the _13C produced by our pyrolysis technique. Our data indicate that an average 4.3. +/-0.5. (V-PDB) apparent isotopic fractionation accompanies the pyrolysis extractions. We postulate that this isotope offset could be the result of incomplete thermal desorption during pyrolysis. We are continuing to investigate the reliability of this pyrolysis technique for correcting carbon isotope measurements of mineral surface catalyzed organic compounds.

Socki, Richard A.↗

Methods for lignin depolymerization using thiols

The disclosure relates to a method for depolymerizing lignin. The method includes reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting. The method can further include forming an oxidized thiol reaction product between two thiol groups from one or more thiol compounds, and then reducing the oxidized thiol reaction product to re-form or regenerate the thiol compound for further lignin depolymerization.

09 BIOMASS FUELS↗

COSP - A computer model of cyclic oxidation

A computer model useful in predicting the cyclic oxidation behavior of alloys is presented. The model considers the oxygen uptake due to scale formation during the heating cycle and the loss of oxide due to spalling during the cooling cycle. The balance between scale formation and scale loss is modeled and used to predict weight change and metal loss kinetics. A simple uniform spalling model is compared to a more complex random spall site model. In nearly all cases, the simpler uniform spall model gave predictions as accurate as the more complex model. The model has been applied to several nickel-base alloys which, depending upon composition, form Al2O3 or Cr2O3 during oxidation. The model has been validated by several experimental approaches. Versions of the model that run on a personal computer are available.

Lowell, Carl E.↗

Universal Behavior of a Cyclic Oxidation Model

A mathematical model has been generated to represent the iterative, discrete growth and spallation processes associated with cyclic oxidation. Parabolic growth kinetics (k(sub p)) over and a constant spall area (F(sub A)) were assumed, with spalling occurring interfacially at the thickest regions of the scale. Although most models require numerical techniques, the regularity and simplicity of this progression permitted an approximation by algebraic expressions. Normalization could now be performed to reflect all parametric effects, and a universal cyclic oxidation response was generated: W(sub u) = 1/2 {3J(sub u)(sup 1/2)+ J(sub u)(sup 3/2)} where W, is weight change normalized by the maximum and J(sub u) is the cycle number normalized by the number to reach maximum. Similarly, the total amount of metal consumed was represented by a single normalized curve. The factor [(S(sub c)-l)(raised dot)sqrt(F(sub A)k(sub p)DELTAt)] was identified as a general figure of merit, where S(sub c) is the mass ratio of oxide to oxygen and DELTAt is the cycle duration. A cyclic oxidation failure map was constructed, in normalized k(sub p)-F(sub A) space, as defined by the locus of points corresponding to a critical amount of metal consumption in a given time. All three constructions describe behavior for every value of growth rate, spall fraction, and cycle duration by means of single curves, but with two branches corresponding to the times before and after steady state is achieved.

Smialek, James L.↗

Benzoic acid degradation of polyacrylonitrile fibers

The reactions of polyacrylonitrile (PAN) fibers in the presence of benzoic acid have been studied. Polyacrylonitrile fibers oxidize more readily in the presence of benzoic acid than in air at temperatures in the range of 170 C. The product decreased in solubility with extent of reaction. Gel permeation chromatography of the soluble fraction showed change in polydispersity. The insoluble product exhibited differences in weight loss as a function of decomposition temperature compared to PAN fibers. Infrared analyses of the fiber product showed absorption peaks similar to air-oxidized PAN. High-energy photoelectron spectral analysis showed a carbon-rich surface which contained oxygen and nitrogen. An air oxidized sample of fiber contained more oxygen at the surface than a fiber treated first with benzoic acid and then air oxidized.

Varma, D. S.↗