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At least 217 records · Page 12

Evaluation of moisture barrier coatings on carbon-phenolic SRM nozzle materials

The carbon-phenolic composite ablative material used on the Solid Rocket Motor (SRM) nozzle is known to absorb moisture from the atmosphere. This could cause problems such as pocketing during firing. Several moisture barrier coatings were tested on the SRM nozzle material. Data are presented for six of the 12 coatings to be tested. The data were obtained from immersion of coated samples in an environmental chamber at 100 F and 100% relative humidity and by using a modified TGA (thermal gravimetric analysis) technique. The TGA technique involved allowing wet nitrogen (25 C, 80% relative humidity) to flow across a small sample at about 65 cu cm per minute while continually monitoring the weight increase. These preliminary results show Kel-F-800, a material supplied by 3M Corporation to be the better moisture barrier. A second task was to collect data on the relative absorption of water and kerosene into the carbon-phenolic SRM nozzle material. These data indicate that water absorbs into the nozzle material to a much greater extent than kerosene. Thus kerosene is the more likely solvent in which to make specific gravity measurements on the SRM nozzle material.

Mcnutt, Ronald C.↗

Areas of Seal R/D at GE

About four years ago, work was completed on a 36 inch diameter gas to gas carbon ring seal used to buffer low pressure turbine air at the rim of the forward outer flowpath on the GE36 unducted fan (UDF) engine. At about the same time, we were developing a long life counter-rotating intershaft air-oil seal of approximately 7.6 inch diameter for operation at 800 fps, 800 F, and 50 psid. Although we were successful in meeting most program goals with a split ring seal of the axial bushing type, the seal with the greatest payoff in life and air leakage rates, bearing many features in common with the GE36 seal, could not be successfully tested because of the structural weakness of the primary seal ring carbon material. This was a split ring seal using a hybrid combination of orifice compensated hydrostatic and shrouded hydrodynamic gas bearings. We are presently working to develop this design in conjunction with high strength materials being developed by Pure Carbon Co. In the area of engine secondary gas flow path-sealing for performance improvement, we are currently working with carbon and all metal face seals. A 15 inch diameter all metal 'aspirating' face seal, using self-acting hydrostatic bearings, was successfully tested to 700 fps, 100 psid, and 1000 F, demonstrating long life at flow reduction of 86 percent compared to a 'best' labyrinth. This seal will be developed through 1400 F, 900 fps, and 350 psid. The seal 'aspirates' closed at about idle speed pressure during engine start and reopens at engine shutdown. A hydraulic thrust balance seal, currently using orifice compensated hydrostatics, is under development. Other aspects of these projects are briefly covered.

Pope, A. Nelson↗

Effects of Atomic-Scale Structure on the Fracture Properties of Amorphous Carbon - Carbon Nanotube Composites

The fracture of carbon materials is a complex process, the understanding of which is critical to the development of next generation high performance materials. While quantum mechanical (QM) calculations are the most accurate way to model fracture, the fracture behavior of many carbon-based composite engineering materials, such as carbon nanotube (CNT) composites, is a multi-scale process that occurs on time and length scales beyond the practical limitations of QM methods. The Reax Force Field (ReaxFF) is capable of predicting mechanical properties involving strong deformation, bond breaking and bond formation in the classical molecular dynamics framework. This has been achieved by adding to the potential energy function a bond-order term that varies continuously with distance. The use of an empirical bond order potential, such as ReaxFF, enables the simulation of failure in molecular systems that are several orders of magnitude larger than would be possible in QM techniques. In this work, the fracture behavior of an amorphous carbon (AC) matrix reinforced with CNTs was modeled using molecular dynamics with the ReaxFF reactive forcefield. Care was taken to select the appropriate simulation parameters, which can be different from those required when using traditional fixed-bond force fields. The effect of CNT arrangement was investigated with three systems: a single-wall nanotube (SWNT) array, a multi-wall nanotube (MWNT) array, and a SWNT bundle system. For each arrangement, covalent bonds are added between the CNTs and AC, with crosslink fractions ranging from 0-25% of the interfacial CNT atoms. The SWNT and MWNT array systems represent ideal cases with evenly spaced CNTs; the SWNT bundle system represents a more realistic case because, in practice, van der Waals interactions lead to the agglomeration of CNTs into bundles. The simulation results will serve as guidance in setting experimental processing conditions to optimize the mechanical properties of CNT composites.

Jensen, Benjamin D.↗

Carbon-carbon composites: Emerging materials for hypersonic flight

An emerging class of high temperature materials called carbon-carbon composites are being developed to help make advanced aerospace flight become a reality. Because of the high temperature strength and low density of carbon-carbon composites, aerospace engineers would like to use these materials in even more advanced applications. One application of considerable interest is as the structure of the aerospace vehicle itself rather than simply as a protective heat shield as on Space Shuttle. But suitable forms of these materials have yet to be developed. If this development can be successfully accomplished, advanced aerospace vehicles such as the National Aero-Space Plane (NASP) and other hypersonic vehicles will be closer to becoming a reality. A brief definition is given of C-C composites. Fabrication problems and oxidation protection concepts are examined. Applications of C-C composites in the Space Shuttle and in advanced hypersonic vehicles as well as other applications are briefly discussed.

Maahs, Howard G.↗

TRANSTRAIN: A program to compute strain transformations in composite materials

Over the years, the solid rocket motor community has made increasing use of composite materials for thermal and structural applications. This is particularly true of solid rocket nozzles, which have used carbon phenolic and, increasingly, carbon-carbon materials to provide structural integrity and thermal protection at the high temperatures encountered during motor burn. To evaluate the degree of structural performance of nozzles and their materials and to verify analysis models, many subscale and full-scale tests are run. These provide engineers with valuable data needed to optimize design and to analyze nozzle hardware. Included among these data are strains, pressures, thrust, temperatures, and displacements. Recent nozzle test hardware has made increasing use of strain gauges embedded in the carbon composite material to measure internal strains. In order to evaluate strength, these data must be transformed into strains along the fiber directions. The fiber-direction stresses can then be calculated. A computer program written to help engineers correctly manipulate the strain data into a form that can be used to evaluate structural integrity of the nozzle is examined.

Ahmed, Rafiq↗

Selective pseudocapacitive immobilization of REE elements on carbon based electrodes

Current extraction technologies for rare earth elements at ambient conditions are reagent and energy intensive, giving rise to significant quantities of secondary waste streams. Exploration of the removal of common cations from aqueous streams has been undertaken with carbon materials and have shown promising results. However, those promising materials have not been explored extensively for rare earth element capture from aqueous process streams. In this study, a carbon electrode was investigated for the adsorption and immobilization of REE elements from aqueous solutions. Cyclic voltammetry studies of the carbon electrode displayed a pseudocapacitive behavior where it was verified that cation adsorption is accompanied by an electron transfer process. Preliminary tests showed that a current density of 89.1 mA. g -1 , allowed for the pseudocapacitive adsorption (PSA) of Nd 3+ cation without the formation of rare earth hydroxides. Hence, the selective PSA of Nd 3+ was verified in an electrolyte solution with equimolar concentrations of Nd 3+ , Mg 2+ , Li + , Na + and K + , achieving separation factors of 8.6, 1.1, and 10.9 for Nd 3+ /Li + , Nd 3+ /Na + , and Nd 3+ /Mg 2+ , respectively. Analysis of the potential-time curves for the various cations suggests that storage of ions in the electrode involved pore-spacings rather than interlayer spacings and was corroborated by XRD analysis. Specific capacitance as high as >640 F.g -1 for Nd 3+ was also observed for the carbon electrode, with Faradaic efficiencies (FE) of > 20% for Nd 3+ and Mg 2+ , and > 9% for Na + . Furthermore, adsorption capacity of >125 mg g -1 after 4hrs of electrosorption was observed for Nd 3+ . In the presence of the Nd 3+ electrolyte, the electrode achieved increasing storage of Nd 3+ with >94% retention of Nd 3+ with a FE > 20% over 6 cycles between loading and releases in 1 M KCl solution. In conclusion, these preliminary results provide information and some guidance on the selective recovery of rare earth elements, such as Nd, in aqueous streams in the presence of competitive cations employing the use of carbon-based materials.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Towards low-carbon low-energy concrete alternatives: Life cycle assessment of carbonated cementitious material-based precast panels

Cement is responsible for 22 % of all global CO 2 emissions from industrial processes. Technological innovation for developing and deploying of alternative materials will be required to decarbonize the cement industry. Carbonated cementitious materials (CCMs) are building materials that rely on carbon mineralization for their strength. A process-based cradle-to-gate life cycle assessment (LCA) was conducted to evaluate the global warming potential (GWP), cumulative energy demand, and water consumption of a lab-scale CCM-based precast panel compared to a conventional precast concrete panel. Since the CCM process is currently a lab-scale early-stage process, the CCM panel showed higher environmental impacts compared to the conventional panel. However, scenario analyses include mature production process scenarios. In conclusion, a sensitivity analysis revealed that the GWP of CCM can be lowered to below that of the conventional panel using polymers, fillers, low-carbon electricity sources, and optimized carbonation parameters.

36 MATERIALS SCIENCE↗

Nanoporous weakly coordinating anionic frameworks (Final Technical Report)

Under this award, we synthesized and characterized new weakly coordinating, anionic covalent organic frameworks. The motivation was to expand the class of covalent organic frameworks though the introduction of the first weakly coordinating anionic ones. The significance of the weakly coordinating anionic character of these frameworks is associated with the character of the counter (metal) cations in their pores. Those counter-cations, due to the inability to effectively coordinate to the pore walls, have a “naked”, and thus highly electrophilic, Lewis acidic character. Such properties are expected to translate to a number of interesting physical properties that can be potentially used for a range of energy-relevant applications. One of these applications is gas adsorption, separation, and storage. The electrophilic, Lewis acidic character of the counter-cations are expected to strongly bind to gas molecules entering the pores leading to higher gas sorption capacities. Other applications include heterogeneous catalysis, ion exchange, and solid state ion conduction. Within the project we explored a range of chemical blocks, and tested synthesis conditions to polymerize these building blocks to form the target materials. In particular, we focused on materials with group 15 elements like phosphorus in the oxidation state +5 and the coordination number 6, that have a formal -1 charge. The synthesis of such materials is challenging because its success depends on the absence of residual monomeric and oligomeric side-products in the pores, and the absence of significant framework interpenetration. Crystalline forms of these materials require sufficient reversibility of the polymerization reaction (which is difficult to achieve because group 15 elements like P tend to make strong covalent bonds with neighbored elements), as well as suitable polymerization rates that prevent the formation of kinetically controlled products. We had success with the preparation of anionic porous organic frameworks with anionic building blocks containing P(V)O6 octahedra synthesized through Yamamoto coupling reactions. These materials are non-crystalline because of the irreversible nature of the Yamamoto coupling reaction, but show porosity. The porosity and surface area can be significantly increased by co-reaction with electrostatically neutral co-reactants. Very high porosity and surface areas can be achieved when the materials are washed with hydrochloric acid. This method is commonly used to free products from Yamamoto coupling reactions from by-products. Indeed, this method removed by products from the pores of our materials, however it also led to the hydrolysis of the PO6 octahedra to form pending phosphonic acid groups (-PO3H)-groups in the frameworks (PA-POFs) which was actually not desired. Nonetheless, these materials showed high CO2 sorption capacities. In addition, they show extremely high (actually record) sorption capacities for the removal of a range of common micropollutants such as bisphenol A (BPA) and 4-nitrophenol in water. BPA is a wide-spread organic pollutant and a known endocrine disruptor. The maximum adsorption capacity of BPA at equilibrium is found to be as high as 3,366 mg g-1 by Langmuir adsorption model, which is more than 10 times greater than peer materials. The polymer also rapidly removes various other organic micropollutants with more than 90% removal efficiencies. In addition, the PA-POF material can be regenerated at least five times by mild washing using methanol without significant loss in removal efficiency. This is significant advantage over commonly used activated carbon materials (that are in Brita water faucet filters, for example). Comparison studies showed that only materials with the phosphonate groups show extreme sorption although the number of PA group is actually small according to solid state NMR and EDX data. More research would be needed to investigate why this is (a possibility is that the phosphonate groups have a multiplying effect in which a PA-induced initial adsorption leads to the adsorption of much more adsorbate). The extreme sorption capabilities can also be visually seen when colored adsorbates such as 4-nitrophenol are used, as the adsorption of the nitrobenzene leads to the decoloration of the solution. We have produced three short videos that illustrate the sorption capabilities compared to two peer materials (activated carbon from dismantled Brita water filters, and a electrostatically neutral, chemically related, porous organic polymer, respectively).

36 MATERIALS SCIENCE↗

Size-Dependent Energy of Ni Nanoparticles on Graphene Films on Ni(111) and Adhesion Energetics by Adsorption Calorimetry

The use of carbon supports for late transition-metal nanoparticle catalysts has grown substantially in recent years due to efforts to develop electrocatalysts for clean energy applications and catalysts for new aqueous-phase biomass-related conversions and due to the evolution of new carbon materials with unique properties (e.g., graphene, carbon nanotubes, and so forth). However, much less is known about the bonding energetics of catalytic metal nanoparticles on carbon supports in comparison with oxide supports, which are more common for thermal catalysis. Here, we report the growth morphology and heats of adsorption of Ni vapor deposited onto graphene/Ni(111) at 300 K and 100 K using metal vapor single-crystal adsorption calorimetry and He + low-energy ion scattering (LEIS). These results provide the Ni chemical potential versus particle size, and the Ni/graphene adhesion energy. LEIS intensities suggest that Ni grows as flat-topped face-centered cubic islands with a nearly constant thickness of ~1.5 nm when deposited at 300 K. At 100 K, Ni grows as smaller nanoparticles, well modeled as hemispherical hexagonal close-packed nanoparticles with a density of ~2 × 10 16 particles/m 2 . The Ni chemical potential as a function of average particle diameter in the 0.5 to 4 nm range at 100 K was determined from the heats of Ni gas adsorption. Further, by fitting the measured chemical potential as a function of diameter, we determined an adhesion energy of 3.6 J/m 2 for large Ni particles on graphene/Ni(111). This adhesion energy is in good agreement with previous scanning tunneling microscopy and density functional theory investigations of Ni/graphene/Ni(111).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reactor engineering for converting CO 2 to solid carbon

Converting CO 2 into solid carbon materials provides both long-term carbon sequestration and the production of value-added products. Here, this Comment compares reactor configurations guided by thermodynamic analysis, evaluates the market volume and morphology control of different carbon products, and identifies hurdles and opportunities for scaled-up deployment.

58 GEOSCIENCES↗

Methods for producing metal carbide materials

Methods of producing silicon carbide, and other metal carbide materials. The method comprises reacting a carbon material (e.g., fibers, or nanoparticles, such as powder, platelet, foam, nanofiber, nanorod, nanotube, whisker, graphene (e.g., graphite), fullerene, or hydrocarbon) and a metal or metal oxide source material (e.g., in gaseous form) in a reaction chamber at an elevated temperature ranging up to approximately 2400° C. or more, depending on the particular metal or metal oxide, and the desired metal carbide being produced. A partial pressure of oxygen in the reaction chamber is maintained at less than approximately 1.01×102 Pascal, and overall pressure is maintained at approximately 1 atm.

Garnier, John E.↗

Influence of Polymer and Support Interactions on the Electrocatalytic Properties of Heterogenized Molecular Complexes

Heterogenized molecular catalysts have been the subject of increasing interest in the context of electrochemical small molecule activation due to the possibility of active site homogeneity and tunability, which can surpass many nanostructured materials. When molecular catalysts strongly interact with carbon supports through π–π interactions, they tend to show higher selectivity and activity during heterogeneous electrochemical reactions. Indeed, ligand modifications in the secondary sphere that allow for more π–π overlap between catalyst and carbon support often show improved performance. Interactions between catalyst and polymer binder are also a possible modulus of control in these reactions, either through coordinating moieties that interact with active sites or through control over substrate or product transport. Finally, the covalent linking of molecular complexes onto carbon materials has also been shown to result in high activity and stability. Recent advances in the use of carbon supports, both through covalent and non-covalent interactions, and polymers to alter small molecule activation by heterogenized molecular catalysts are summarized in this Perspective.

Johnson, Elizabeth K. [University of Virginia, Cha↗

Current research in oxidation-resistant carbon-carbon composites at NASA. Langley Research Center

The significant potential of carbon-carbon composites for high-temperature structural applications is well established. For hypersonic vehicle applications, desirable properties include low density, high specific strength and stiffness, low coefficients of thermal expansion, and retention of mechanical properties above 3000 F. A significant problem associated with carbon materials, however, is that they oxidize rapidly in air at temperatures above about 800 F, and therefore must be protected from oxidation. Successful development of effective methods of oxidation protection is key to the eventual utilization of carbon-carbon composites on hypersonic vehicles such as NASP. In this presentation, the basic elements of an oxidation-protection system are described. Results from oxidation-performance evaluations of state-of-the-art ACC-4 type material in simulated airframe vehicle environments (temperature, pressure, and time) conducted at NASA Langley are also presented. NASA Langley has an active research effort to improve the oxidation resistance of carbon-carbon materials for airframe structural and vehicle thermal protection applications. Conversion coating and sealant development research is highlighted.

Ohlhorst, Craig W.↗

Recent Progress in Transparent Conductive Materials for Photovoltaics

Transparent conducting materials (TCMs) are essential components for a variety of optoelectronic devices, such as photovoltaics, displays and touch screens. In recent years, extensive efforts have been made to develop TCMs with both high electrical conductivity and optical transmittance. Based on material types, they can be mainly categorized into the following classes: metal oxides, metal nanowire networks, carbon-material-based TCMs (graphene and carbon nanotube networks) and conjugated conductive polymers (PEDOT:PSS). This review will discuss the fundamental electrical and optical properties, typical fabrication methods and the applications in solar cells for each class of TCMs and highlight the current challenges and potential future research directions.

14 SOLAR ENERGY↗

Segmentation of Lightweight Ablator Micro-Tomography Using Deep Learning

Ablative thermal protection systems (TPS) are essential for high speed entry of planetary atmospheres, such as those of Earth and Mars. Upon entry the kinetic energy of the spacecraft is converted into thermal energy, leading to high heat fluxes at the wall of the craft. Because of this extreme heating, a robust ablative TPS material must be selected. A common material selection today is phenolic-impregnated carbon ablator (PICA), which is a low-density carbon material known for producing dust that is not suitable to a cleanroom environment. To mitigate dust created by a PICA heatshield, a silicone-based spray called NuSil is applied to the surface of the TPS, creating PICA-NuSil (PICA-N). PICA-N has been observed to have a different material response from regular PICA during high enthalpy flow testing, producing surface temperatures up to 200K less than those seen for PICA [1]. To better understand this phenomenon, it is critical that robust methods of PICA-N material characterization are developed. The purpose of this project is to investigate Object Research Systems’ (ORS) Dragonfly deep learning tools as a means of accurately segmenting and characterizing PICA-N. Systematic testing of this software has shown that Dragonfly deep learning tools have strong potential for accurate segmentation/ characterization of PICA-N and other TPS materials.

Micro-tomography↗

Portable quantitative confocal Raman spectroscopy: Non-destructive approach of the carbonation chemistry and kinetics

Highlights: • Raman spectroscopy was used to monitor carbonation of portlandite • The approach was non-destructive, continuous, and performed within the material • Carbonation was identified coupling Raman spectroscopy and chemometrics • Kinetics was calculated for one portlandite thickness at different CO{sub 2}-percentages Carbonation is one major alteration process of cementitious materials. It can be monitored through several methods, all destructive. In this study, some preliminary investigations were conducted to monitor the carbonation process of pure portlandite with an in situ and non-destructive spectroscopic method. This complementary approach was motivated by a literature review indicating the benefits of Raman spectroscopy, but requiring innovative approaches for data acquisition and analysis. The material was selected to validate this spectroscopic monitoring, coupled with chemometrics tools to allowing an early detection of the carbonation reaction through a structure identified in the spectra data population. The carbonation occurred abruptly, and spectra analysis indicated the occurrence of phases synonymous of microstructural evolutions. Varying the atmospheric percentage of CO{sub 2} (0.04% - 4%) conducted to an appreciation of the kinetics of the carbonation front through the same thickness of portlandite.

36 MATERIALS SCIENCE↗

Microwave-driven synthesis and modification of nanocarbons and hybrids in liquid and solid phases

Over the past 20 years, nanocarbons have become more significant as nanostructured fillers in composites and, more recently, as functional elements in a brand-new class of hybrid materials. Microwave-assisted synthesis and processing is a burgeoning subject matter in materials research with significant strides in the realm of nanocarbon during the last decade. Here, the review examines recent approaches to producing various nanocarbons using microwaves as energy sources, the characterization of such materials for various applications, and their results. The underlying factors supporting the increased performance of such materials or their composites are analyzed and reaction mechanisms are presented wherever necessary. In particular, the recently developed and verified approaches to produce porous carbon materials, CNTs and fibers, carbon nanospheres, carbon dots, CQDs, reduced graphene oxide, nanocarbon hybrid materials, and the purification and modification of CNTs are discussed. The reduction of graphene oxide and the preparation of graphene derivative hybrids using solid-state and liquid-state routes such as polyopl, mixed solvents, ionic liquids, and microwave-assisted hydrothermal/solvothermal methods are analyzed in detail. In addition, the principles of microwave heating in liquid and solid states, the use of metals particles as arcing agents or catalysts, and carbonaceous materials as internal or external susceptors during synthesis and modifications are presented in detail.

25 ENERGY STORAGE↗