Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Graphite Oxidation”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 901 records · Page 50
All sourcesNASA NTRSDOE OSTI
NASA NTRS2012

Carbon Nanotube Bonding Strength Enhancement Using Metal "Wicking" Process

Carbon nanotubes grown from a surface typically have poor bonding strength at the interface. A process has been developed for adding a metal coat to the surface of carbon nano tubes (CNTs) through a wicking process, which could lead to an enhanced bonding strength at the interface. This process involves merging CNTs with indium as a bump-bonding enhancement. Classical capillary theory would not normally allow materials that do not wet carbon or graphite to be drawn into the spacings by capillary action because the contact angle is greater than 90 degrees. However, capillary action can be induced through JPL's ability to fabricate oriented CNT bundles to desired spacings, and through the use of deposition techniques and temperature to control the size and mobility of the liquid metal streams and associated reservoirs. A reflow and plasma cleaning process has also been developed and demonstrated to remove indium oxide, and to obtain smooth coatings on the CNT bundles.

Lamb, James L.↗
DOE OSTI2019

Synergistic Effects of Nano-zinc Oxide on Improving the Flame Retardancy of EVA Composites with an Efficient Triazine-Based Charring Agent

The synergistic effect of nano-zinc oxide (nano-ZnO) on the flame retardancy and thermal stability of intumescent flame retardant ethylene–vinyl acetate (EVA/IFR) consisting of novel hyperbranched triazine-based charring agent (HTCFA) and APP was evaluated by limiting oxygen index (LOI), UL-94 measurement, cone calorimeter test (CCT) and thermogravimetric analysis (TGA), and the residue analysis was also carried out through scanning electron microscopy (SEM), fourier transform infrared (FTIR), laser raman spectroscopy (LRS), and X-ray photoelectron spectroscopy (XPS). The results showed that introducing a certain amount of nano-ZnO could obviously enhance LOI value and UL-94 rating, and effectively restrain the combustion performance of EVA/IFR composites, leading to the decrease of heat and smoke release. The addition of 0.5 wt% nano-ZnO into EVA/IFR composite obtained the highest catalytic effectivity (CAT-EFF). TGA results uncovered a distinct synergistic carbonization effect existed between nano-ZnO and IFR, and nano-ZnO could obviously improve the high-temperature thermal stability and promote the char formation of IFR and EVA/IFR. Analysis of final char residues proved that the incorporation of appropriate amount of nano-ZnO contributed to remaining more P and forming more high-quality graphitization char layers with richer P–O–C and P–N cross-linking structures in condensed phase owing to the catalytic carbonization effect of nano-ZnO on IFR system, which played a critical role in remarkable improvement of flame retardancy and smoke suppression properties of composites.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2020

Titanium Niobium Oxide: From Discovery to Application in Fast-Charging Lithium-Ion Batteries

Lithium-ion batteries are essential for portable technology and are now poised to disrupt a century of combustion-based transportation. The electrification revolution could eliminate our reliance on fossil fuels and enable a clean energy future; advanced batteries would facilitate this transition. However, owing to the demanding performance, cost, and safety requirements, it is challenging to translate new materials from laboratory prototypes to industrial-scale products. This Perspective describes that journey for a new lithium-ion battery anode material, TiNb 2 O 7 (TNO). TNO is intended as an alternative to graphite or Li 4 Ti 5 O 12 with better rate and safety characteristics than the former and higher energy density than the latter. The high capacity of TNO stems from the multielectron redox of Nb 5+ to Nb 3+ , its operating voltage window well above the Li + /Li reduction potential prevents lithium dendrite formation, and its open crystal structure leads to high-power performance. Nevertheless, the creation of a practical TNO anode was nonlinear and nontrivial. Its history is built on 30 years of fundamental science that preceded its application as a battery anode, and its battery development included a nearly 30-year gap. The insights and lessons contained in this Perspective, many of them acquired firsthand, serve two purposes: (i) to unite the disparate studies of TiNb 2 O 7 into a coherent modern understanding relevant to its application as a battery material and (ii) to highlight briefly some of the challenges faced when scaling up a new material that affect TiNb 2 O 7 as well as new electrode candidates more generally.

25 ENERGY STORAGE↗
NASA NTRS1985

The 371 deg C mechanical properties of graphite/polyimide composites

A series of condensation polyimides based on pyromellitic dianhydride is synthesized and evaluated for potential application at 371 C. Several three-and four-ring benzenoid diamine systems containing oxygen bridging groups are investigated. Thermomechanical analysis of neat resin specimens indicate that the polyimide prepared from the dimethyl ester of pyrometallitic acid (PMDE) and 2,2-bis4-(4'-aminophenoxy) phenyl]-1,1,1,3,3,3- hexafluoropropane (BDAF) is the only resin system which has a glass transition temperature (Tg) above 371 C. The Tg of the PMDE/BDAF polyimide is found to be 390 C after a postcure air at 371 C for 24 hr. Unidirectional composites are fabricated from the PMDE/BDAF system and unsized Celion 6000 graphite fibers. Final cure temperatures in the range of 371 to 427 C with an applied pressure of 10.34 to 13.78 MPa are investigated. The void content of the composites ranges from 4.6 to 8.6 percent. Composites cured at 399 C under a pressure of 10.34 MPa and postcured in air at 371 C for 24 hr exhibit the highest 371 C interlaminar shear strength (ILSS, 40.7 MPa) and flexural strength (758 MPa). The thermo-oxidative stability of the composites is determined by subjecting specimens to isothermal exposure at 371 C in air at atmospheric pressure, as well as a pressure of 0.52 MPa. Specimens exposed at atmospheric pressure exhibit a weight loss of 12 percent after 200 hr of exposure and 88 percent retention of its original 371 C ILSS. In contrast, the specimens exposed at 0.52 MPa pressure exhibit a comparable weight loss after only 72 hr, and a 71 percent retention of its original 371 C ILSS.

Delvigs, P.↗
NASA NTRS2004

Ultrasensitive Label-free Electronic Chip for DNA Analysis Using Carbon Nanotube Nanoelectrode Arrays

There is a strong need for faster, cheaper, and simpler methods for nucleic acid analysis in today s clinical tests. Nanotechnologies can potentially provide solutions to these requirements by integrating nanomaterials with biofunctionalities. Dramatic improvement in the sensitivity and multiplexing can be achieved through the high-degree miniaturization. Here, we present our study in the development of an ultrasensitive label-free electronic chip for DNA/RNA analysis based on carbon nanotube nanoelectrode arrays. A reliable nanoelectrode array based on vertically aligned multi-walled carbon nanotubes (MWNTs) embedded in a SiO2 matrix is fabricated using a bottom-up approach. Characteristic nanoelectrode behavior is observed with a low-density MWNT nanoelectrode array in measuring both the bulk and surface immobilized redox species. The open-end of MWNTs are found to present similar properties as graphite edge-plane electrodes, with a wide potential window, flexible chemical functionalities, and good biocompatibility. A BRCA1 related oligonucleotide probe with 18 bases is covalently functionalized at the open ends of the MWNTs and specifically hybridized with an oligonucleotide target as well as a PCR amplicon. The guanine bases in the target molecules are employed as the signal moieties for the electrochemical measurements. Ru(bpy)3(2+) mediator is used to further amplify the guanine oxidation signal. This technique has been employed for direct electrochemical detection of label-free PCR amplicon through specific hybridization with the BRCAl probe. The detection limit is estimated to be less than approximately 1000 DNA molecules, approaching the limit of the sensitivity by laser-based fluorescence techniques in DNA microarray. This system provides a general electronic platform for rapid molecular diagnostics in applications requiring ultrahigh sensitivity, high-degree of miniaturization, simple sample preparation, and low- cost operation.

Li, Jun↗
DOE OSTI2017

Effect of reactor radiation on the thermal conductivity of TREAT fuel

The Transient Reactor Test Facility (TREAT) at the Idaho National Laboratory is resuming operations after more than 20 years in latency in order to produce high-neutron-flux transients for investigating transient-induced behavior of reactor fuels and their interactions with other materials and structures. A parallel program is ongoing to develop a replacement core in which the fuel, historically containing highly-enriched uranium (HEU), is replaced by low-enriched uranium (LEU). Both the HEU and prospective LEU fuels are in the form of UO 2 particles dispersed in a graphite matrix, but the LEU fuel will contain a much higher volume of UO 2 particles, which may create a larger area of interphase boundaries between the particles and the graphite. This may lead to a higher volume fraction of graphite exposed to the fission fragments escaping from the UO 2 particles, and thus may induce a higher volume of fission-fragment damage on the fuel graphite. In this work, we analyzed the reactor-radiation induced thermal conductivity degradation of graphite-based dispersion fuel. A semi-empirical method to model the relative thermal conductivity with reactor radiation was proposed and validated based on the available experimental data. Prediction of thermal conductivity degradation of LEU TREAT fuel during a long-term operation was performed, with a focus on the effect of UO 2 particle size on fission-fragment damage. Lastly, the proposed method can be further adjusted to evaluate the degradation of other properties of graphite-based dispersion fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2015

Highly dispersed buckybowls as model carbocatalysts for C–H bond activation

Buckybowl fractions dispersed on mesoporous silica constitute an ideal model for studying the catalysis of graphitic forms of carbon since the dispersed carbon nanostructures contain a high ratio of edge defects and curvature induced by non-six-membered rings. Dispersion of the active centers on an easily accessible high surface area material allowed for high density of surface active sites associated with oxygenated structures. This report illustrates a facile method of creating model polycyclic aromatic nano-structures that are not only active for alkane C-H bond activation and oxidative dehydrogenation but also can be practical catalysts to be eventually used in industry.

36 MATERIALS SCIENCE↗
DOE OSTI2020

A Surface Se-Substituted LiCo[O 2-δ Se δ ] Cathode with Ultrastable High-Voltage Cycling in Pouch Full-Cells

Cycling LiCoO 2 to above 4.5 V for higher capacity is enticing; however, hybrid O anion- and Co cation-redox (HACR) at high voltages facilitates intrinsic O α - (α < 2) migration, causing oxygen loss, phase collapse, and electrolyte decomposition that severely degrade the battery cyclability. Hereby, commercial LiCoO 2 particles are operando treated with selenium, a well-known anti-aging element to capture oxygen-radicals in the human body, showing an “anti-aging” effect in high-voltage battery cycling and successfully stopping the escape of oxygen from LiCoO 2 even when the cathode is cycled to 4.62 V. Furthermore, ab initio calculation and soft X-ray absorption spectroscopy analysis suggest that during deep charging, the precoated Se will initially substitute some mobile O α - at the charged LiCoO 2 surface, transplanting the pumped charges from O α - and reducing it back to O 2- to stabilize the oxygen lattice in prolonged cycling. As a result, the material retains 80% and 77% of its capacity after 450 and 550 cycles under 100 mA g -1 in 4.57 V pouch full-cells matched with a graphite anode and an ultralean electrolyte (2 g Ah -1 ).

36 MATERIALS SCIENCE↗
DOE OSTI2025

Methodology of Atomic Force Microscopy Visualization of Electrode–Electrolyte Interfaces

Electrochemical atomic force microscopy (EC-AFM) provides unprecedented insights into the microstructure of electrode–electrolyte interfaces during electrochemical reactions. However, performing EC-AFM measurements has many challenges, for example, drift, contamination, and probe degradation. We present solutions to these experimental issues through electrochemical cell design and carefully chosen experimental parameters. The possibility that the probes can react with the interface during scanning, generating false-positive electrochemical dynamics, is discussed as an example of the challenge of high-fidelity EC-AFM measurement. Here, we demonstrate this effect in highly ordered pyrolytic graphite and show that we could use electrochemical control of the AFM probe to enable high-fidelity in situ AFM visualization of solid–liquid interfaces during electrochemical reactions.

Electrochemical cells↗
DOE OSTI2017

Quaternary FeCoNiMn-Based Nanocarbon Electrocatalysts for Bifunctional Oxygen Reduction and Evolution: Promotional Role of Mn Doping in Stabilizing Carbon

The intrinsic instability of carbon largely limits its use for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) as a bifunctional catalyst in reversible fuel cells or water electrolyzers. In this paper, we discovered that Mn doping has a promotional role in stabilizing nanocarbon catalysts for the ORR/OER in alkaline media. Stable nanocarbon composites are derived from an inexpensive carbon/nitrogen precursor (i.e., dicyandiamide) and quaternary FeCoNiMn alloy via a template-free carbonization process. In addition to FeCoNiMn metal alloys/oxides, the carbon composites comprise substantial carbon tube forests growing on a thick and dense graphitic substrate. The dense carbon substrate with high degree of graphitization results from Mn doping, while active nitrogen-doped carbon tubes stem from FeCoNi. Catalyst structures and performance are greatly dependent on the doping content of Mn. Various accelerated stress tests (AST) and life tests verify the encouraging ORR/OER stability of the nanocarbon composite catalyst with optimal Mn doping. Extensive characterization before and after ASTs elucidates the mechanism of stability enhancement resulting from Mn doping, which is attributed to (i) hybrid carbon nanostructures with enhanced resistance to oxidation and (ii) the in situ formation of the β-MnO 2 and FeCoNi-based oxides capable of preventing carbon corrosion and promoting activity. Note that the improvement in stability due to Mn doping is accompanied by a slight activity loss due to a decrease in surface area. Finally, this work provides a strategy to stabilize carbon catalysts by appropriately integrating transition metals and engineering carbon structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1993

Solidification of eutectic system alloys in space (M-19)

It is well known that in the liquid state eutectic alloys are theoretically homogeneous under 1 g conditions. However, the homogeneous solidified structure of this alloy is not obtained because thermal convection and non-equilibrium solidification occur. The present investigators have clarified the solidification mechanisms of the eutectic system alloys under 1 g conditions by using the in situ observation method; in particular, the primary crystals of the eutectic system alloys never nucleated in the liquid, but instead did so on the mold wall, and the crystals separated from the mold wall by fluid motion caused by thermal convection. They also found that the equiaxed eutectic grains (eutectic cells) are formed on the primary crystals. In this case, the leading phase of the eutectic must agree with the phase of the primary crystals. In space, no thermal convection occurs so that primary crystals should not move from the mold wall and should not appear inside the solidified structure. Therefore no equiaxed eutectic grains will be formed under microgravity conditions. Past space experiments concerning eutectic alloys were classified into two types of experiments: one with respect to the solidification mechanisms of the eutectic alloys and the other to the unidirectional solidification of this alloy. The former type of experiment has the problem that the solidified structures between microgravity and 1 g conditions show little difference. This is why the flight samples were prepared by the ordinary cast techniques on Earth. Therefore it is impossible to ascertain whether or not the nucleation and growth of primary crystals in the melt occur and if primary crystals influence the formation of the equiaxed eutectic grains. In this experiment, hypo- and hyper-eutectic aluminum copper alloys which are near eutectic point are used. The chemical compositions of the samples are Al-32.4mass%Cu (Hypo-eutectic) and Al-33.5mass%Cu (hyper-eutectic). Long rods for the samples are cast by the Ohno Continuous Casting Process and they show the unidirectionally solidified structure. Each flight and ground sample was made of these same rods. The dimensions of all samples are 4.5 mm in diameter and 23.5 mm in length. Each sample is put in a graphite capsule and then vacuum sealed in a double silica ampoule. Then the ampoule is put in the tantalum cartridge and sealed by electron beam welding. For onbard experiments, a Continuous Heating Furnance (CHF) will be used for melting and solidifying samples under microgravity conditions. Six flight samples will be used. Four samples are hypo-eutectic and two are hyper-eutectic alloys. The surface of the two hypo-eutectic alloy samples are covered with aluminum oxide film to prevent Marangoni convection expected under microgravity conditions. Each sample will be heated to 700 C and held at that temperature for 5 min. After that the samples will be allowed to cool to 500 C in the furnace and they will be taken out of the furnace for He gas cooling. The heating and cooling diagrams for the flight experiments are shown. After collecting the flight samples, the solidified structures of the samples will be examined and the mechanisms of eutectic solidification under microgravity conditions will be determined. It is likely that successful flight experiment results will lead to production of high quality eutectic alloys and eutectic composite materials in space.

Ohno, Atsumi↗
NASA NTRS1995

Magnetic properties of iron-bearing graphite fibers

Carbon fibers containing ferromagnetically-ordered iron or other transition metals could be used in a variety of lightweight magnetic composites. Intercalation of bulk graphite with CoCl2 or FeCl3, followed by reduction with butyl lithium, did indeed produce magnetic samples; however, the observed room temperature permeabilities (mu) were less than 2 G/Oe. Magnetic data are presented on carbon fibers containing large amounts of elemental iron, which were prepared by a new method. In this method Amoco P-75 fibers were intercalated with Br2 and I2 followed by fluorination, forming CF(0.75). This product was then intercalated with FeCl3. Subsequent heat treatments in oxidizing and reducing atmospheres converted most of the iron to the pure alpha phase. Room temperature permeabilities as large as 40 G/Oe are observed.

Ferrante, R.↗
DOE OSTI2018

Thermal Model of the AGR-5/6/7 Experiment

Several fuel and material irradiation experiments have been planned for the U.S. Department of Energy Advanced Gas Reactor Fuel Development and Qualification Program, which supports the development and qualification of tristructural isotropic (TRISO) coated particle fuel for use in high-temperature gas-cooled reactors. The goals of these experiments are to provide irradiation performance data to support fuel process development, qualify fuel for normal operating conditions, support development of fuel performance models and codes, and provide irradiated fuel and materials for post-irradiation examination and safety testing. Originally planned and named as separate fuel experiments, but subsequently combined into a single test train, AGR-5/6/7 will test low-enriched uranium oxycarbide (UCO – a heterogeneous mixture of uranium oxide and uranium carbide) TRISO fuel. The AGR-5/6 portion of the experiment will provide data to support qualification of the selected reference fuel design, while the AGR-7 portion will serve as a margin test, irradiating the fuel beyond normal operating conditions. A thermal finite element model has been created for the five capsules comprising the AGR-5/6/7 experiment. Heat rates from a physics analysis are imported into the model along with fast neutron fluence. Graphite shrinkage due to the fast neutron fluence is incorporated into the model. Gas gaps change as a function of fast neutron fluence. Radiation heat transfer is a major contributor in this model. This is a large model with more than 1 million finite element brick elements. More than 150 different parts are modeled in the finite element model and communicate with each other from a heat transfer sense. More than 50 thermocouples are used in the experiment and are compared to actual measurements. The experiment is composed of five separate stainless steel capsules all welded together. Each capsule has its own Helium/.Neon gas mixture to help control the temperature of the capsule.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

A Low-Voltage Layered Na 2 TiGeO 5 Anode for Lithium-Ion Battery

Titanium-based anode materials have achieved much progress with the wide studies in lithium-ion batteries. However, these known materials usually possess high discharge voltage platforms and limited energy densities. In this work, a titanium-based oxide of Na 2 TiGeO 5 with layered structure, two-dimensional lamellar frame and exposed highly active (001) facet, exhibiting good electrochemical performance in terms of high capacity (410 mAh g –1 with a current density of 50 mA g –1 ), excellent rate capability and cycling stability with no obvious capacity attenuation after 4000 cycles, is reported. The appropriate discharge voltage plateau at around 0.2 V endows the Na 2 TiGeO 5 anode material high security compared with graphite and high energy density compared with spinel Li 4 Ti 5 O 12 . Combining the electrochemical tests and the density functional theory calculations, the Li + storage mechanism of Na 2 TiGeO 5 is elucidated and the conversion reaction process is revealed. More importantly, this study provides a way to develop low-voltage and high-capacity titanium-based anode materials for efficient energy storage.

25 ENERGY STORAGE↗
DOE OSTI2022

Atomic-scale mechanism of carbon nucleation from a deep crustal fluid by replica exchange reactive molecular dynamics simulation

Here we present a mechanistic model of carbon nucleation and growth from a fluid at elevated temperature (T) and pressure conditions, typical of those found in the shallow Earth’s lithosphere. Our model uses a replica exchange reactive molecular dynamics framework in which molecular configurations are swapped between adjacent T replica at regular intervals according to underlying statistical mechanics. This framework allows predicting complex molecular structures and thermodynamics while remaining computationally efficient. Here we simulate the reactivity of an unstable mixture of CO 2 and CH 4 at 1000 K and 1 GPa. We find that the path to thermodynamic equilibrium is initially entropy-driven, producing a diversity of short-lived species, including various alcohols with intermediate carbon oxidation states. Cyclic and polycyclic radicals that are sometimes resonance-stabilized form next and set the stage for carbon nucleation. The carbon exsolution process releases abundant water, is exothermic and starts with the nucleation of a large aggregate of hydrogenated graphene flakes from covalently bonded polycyclic units. The carbon backbone of this nucleus subsequently grows into a hydrogen-depleted fullerene-like structure, before evolving toward a partially bilayered graphene layer. Overall, our results show that the mechanism of graphitic C formation is certainly not bimolecular, and that it may involve a combination of key condensation and radical chain reactions. This will help understand the isotopic, and reactive characteristics of carbon-bearing fluids during their upward transit through the Earth’s mantle and crust. Moreover, the mechanistic insights outlined here present intriguing similarities with the process of soot and interstellar dust formation, which suggests that the widespread distribution of abiotic polyaromatic and graphitic material on Earth and beyond may reflect the prevalence of a fundamental chemical pathway.

58 GEOSCIENCES↗
NASA NTRS1994

Ferric chloride graphite intercalation compounds prepared from graphite fluoride

The reaction between graphite fluoride and ferric chloride was observed in the temperature range of 300 to 400 C. The graphite fluorides used for this reaction have an sp3 electronic structure and are electrical insulators. They can be made by fluorinating either carbon fibers or powder having various degrees of graphitization. Reaction is fast and spontaneous and can occur in the presence of air. The ferric chloride does not have to be predried. The products have an sp2 electronic structure and are electrical conductors. They contain first stage FeCl3 intercalated graphite. Some of the products contain FeCl2*2H2O, others contain FeF3 in concentrations that depend on the intercalation condition. The graphite intercalated compounds (GIC) deintercalated slowly in air at room temperature, but deintercalated quickly and completely at 370 C. Deintercalation is accompanied by the disappearing of iron halides and the formation of rust (hematite) distributed unevenly on the fiber surface. When heated to 400 C in pure N2 (99.99 vol %), this new GIC deintercalates without losing its molecular structure. However, when the compounds are heated to 800 C in quartz tube, they lost most of its halogen atoms and formed iron oxides (other than hematite), distributed evenly in or on the fiber. This iron-oxide-covered fiber may be useful in making carbon-fiber/ceramic-matrix composites with strong bonding at the fiber-ceramic interface.

Hung, Ching-Cheh↗
DOE OSTI2019

Integrated Approach to Fluoride High Temperature Reactor Technology and Licensing Challenges (FHR-IRP)

This document constitutes progress made on this project by the Georgia Tech led Integrated Approach to Fluoride High Temperature Reactor Technology and Licensing Challenges (FHR-IRP). This is the first draft of the project final report. Chapter 3 is focused on Tritium management. Tritium management in Fluoride-salt High-temperature Reactors (FHRs) presents a major operational concern and a significant challenge. Tritium is generated via multiple pathways including various interactions in fuel and structural materials, as well as coolant (primarily interaction with lithium and beryllium), leading to a complex evolution and spatial distribution of tritium generation rate. FHR generates orders of magnitude more tritium than in LWRs, and has potential for a significant release, via permeation through structural materials (due to high temperature), and through heat exchanger(s). Therefore, accurate estimate is necessary. For that purpose relevant tritium production pathways were identified. A methodology to obtain space-time dependent tritium generation rate was developed and implemented, employing SCALE and MCNP codes. Detailed models of the reference Advanced High Temperature Reactor (AHTR) design were developed. A multi-parametric metrics was introduced to capture relevant tritium production indicators, including the instantaneous tritium production rate, total tritium production (neglecting subsequent decay), and accumulated tritium production (accounting for the decay). The obtained results will inform tritium management, including the sizing of the components, and to gain insight on the impact of the core design parameters on tritium generation rates. Research effort on Liquid Salt Impurity Removal, Redox and Corrosion Control is discussed in Chapter 4. Section 4.1 is an introduction chapter. Based on the current available knowledge and operation experience on previous MSRs and other types of nuclear reactors, the report identifies the major impurities that are related to either material compatibility, salt properties or radioactive source terms, and the potential contamination sources of these impurities, their transport in the primary coolant loop and available cleanup methodologies for a particular group of impurity. In section 4.2, the available purification methods were discussed, including the liquid/liquid extraction using liquid Bi-Li which has been applied in MSBR and electrochemical purification which is developed based on Pyroprocessing. In this section, the new multi-stage and multi-salt-component was developed and discussed. Section 4.3 discussed the redox potential control for salt chemistry and corrosion mitigation, including the control theory and the soluble/soluble buffer control method. The section also developed method on how to analyze soluble/soluble redox reaction in a molten salt system and designed an electrochemical sensor for redox potential control. Corrosion models were also reported in this section. Section 4.4 focused on how to measure the fundamental properties in a molten salt. As an example, the section focused on La fluoride in the molten salt. The section developed methods on how analyze electrochemical measurement data to obtain the fundamental properties including the redox potential, diffusion coefficient and exchange current density. All these fundamental information is important for salt purification system development. Section 4.5 focused on measurements of corrosion products in the salts. Because of the different behaviors between Cr and La in the salt, new analysis method for Cr fluorides in the salt was developed. Some results for Fe fluoride in the salt and corrosion measurements were also reported. Section 4.6 demonstrated the separation of oxide from the salt. This section also measured the solubility of La 2 O 3 in the salt as function of temperature. Section 4.7 focused on the separation of La and Ce from the molten salt. These two elements were selected because La was found to be separated by using inert electrode, while for separation of Ce, reactive electrode must be selected. Section 4.8 demonstrated the separation iodine ions from the molten salt. Two kinds of working electrode materials (metal W and graphite) were investigated. Section 4.9 focused on the fundamental data of fission products and actinides in liquid Bi. The chapter reviewed the available data, then based a CALPHAD model, the available data were broadened to the concentration-dependent cases.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
NASA NTRS1973

Ablation of ATJ Graphite at High Temperatures

Results of an extensive experimental program on the ablation of ATJ graphite in air at surface pressures of 0.3 to 4.4 atm and surface temperatures of 2570 to 4030 K are presented. The measured mass-loss rates are correlated with surface temperature, pressure, and effective nose radius. The results are compared with several equilibrium thermochemical ablation theories which differ basically in the chemical species that are considered and in the thermodynamic properties assigned to these species. All the theories predict about the same mass-loss rate in the diffusion-controlled oxidation regime and are in good agreement with the experimental results. At higher temperatures, however, the experimental and theoretical results do not agree. At temperatures above 3700 K, the experimental mass-loss rate becomes independent of pressure and an exponential function of temperature. A comparison of the high-temperature results with the theories indicates that all the theories, except the one based on the thermodynamic properties from the JANAF tables, are invalid because they overpredict the mass-loss rate. On the other hand, the theory based on the JANAF properties underpredicts the measured mass-loss rate by a factor of three at 4000 K. At least a portion of this difference between experiment and theory is attributed to particulate mass loss which is visually observed.

Thermochemical ablation↗