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Janke, Christopher James

Publications and source records attributed to Janke, Christopher James.

At least 19 records

Method of solvent-free manufacturing of composite electrodes incorporating radiation curable binders

A method of making an electrode includes the step of mixing active material particles, radiation curable resin precursors, and electrically conductive particles to create an electrode precursor mixture. The electrode precursor mixture is electrostatically sprayed onto a current collector to provide an electrode preform. The electrode preform is heated and calendered to melt the resin precursor such that the resin precursor surrounds the active particles and electrically conductive particles. Radiation is applied to the electrode preform sufficient to cure the radiation curable resin precursors into resin.

Du, Zhijia↗

Method of solvent-free manufacturing of composite electrodes incorporating radiation curable binders

A method of making an electrode includes the step of mixing active material particles, radiation curable resin precursors, and electrically conductive particles to create an electrode precursor mixture. The electrode precursor mixture is electrostatically sprayed onto a current collector to provide an electrode preform. The electrode preform is heated and calendered to melt the resin precursor such that the resin precursor surrounds the active particles and electrically conductive particles. Radiation is applied to the electrode preform sufficient to cure the radiation curable resin precursors into resin.

25 ENERGY STORAGE↗

Temperature Dependence of Uranium and Vanadium Adsorption on Amidoxime-Based Adsorbents in Natural Seawater

Recent advances in the development of amidoxime-based adsorbents have made it highly promising for seawater uranium extraction. However, there is a great need to understand the influence of temperature on the uranium sequestration performance of the adsorbents in natural seawater. Here in this work, the apparent enthalpy and entropy of the sorption of uranium (VI) and vanadium (V) with amidoxime-based adsorbents were determined in natural seawater tests at 8, 20, and 31 °C that cover a broad range of ambient seawater temperature. The sorption of U was highly endothermic, producing apparent enthalpies of 57 ± 6.0 and 59 ± 11 kJ mol -1 and apparent entropies of 314 ± 21 and 320 ± 36 J K-1 mol -1 , respectively, for two adsorbent formulations. In contrast, the sorption of V showed a much smaller temperature sensitivity, producing apparent enthalpies of 6.1 ± 5.9 and -11 ± 5.7 kJ mol -1 and apparent entropies of 164 ± 20 and 103 ± 19 J K -1 mol -1 , respectively. This new thermodynamic information suggests that amidoxime-based adsorbents will deliver significantly increased U adsorption capacities and improved selectivity in warmer waters. A separate field study of seawater uranium adsorption conducted in a warm seawater site (Miami, FL, USA) confirm the observed strong temperature effect on seawater uranium mining. Lastly, this strong temperature dependence demonstrates that the warmer the seawater where the amidoxime-based adsorbents are deployed the greater the yield for seawater uranium extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Compatibility Assessment of Fuel System Infrastructure Plastics with Bio-oil and Diesel Fuel

We report that bio-oil derived via fast pyrolysis is being developed as a renewable fuel option for petroleum distillates. The compatibility of neat bio-oil with 18 plastic types was evaluated using neat diesel fuel as the baseline. The plastic materials included polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), polyoxymethylene (POM), POM copolymer, high density polyethylene (HDPE), polybutylene terephthalate (PBT), polypropylene (PP), polyethylene terephthalate glycol (PETG), polythiourea (PTU), four nylon grades, and four thermosetting resins. Specimens of each material were immersed in the test fuels for a period of 16 weeks to achieve full saturation. Except for PP and HDPE, the plastic materials underwent higher volume expansion in bio-oil than in the baseline diesel (which was negligible in most cases). This volume increase corresponds to the higher polarity of the bio-oil. PPS, PET, and PTFE were unaffected by bio-oil exposure, but modest swelling (between 2 and 5%) occurred for the two acetals (POM and POM copolymer), Nylon-12, PBT, PETG, and the four resin grades. More moderate swelling (8–15%) was noted for Nylon-6, Nylon-6/6, and Nylon-11, and excessive swell (>40%) occurred for PTU. The nonpolar nature of PP and HDPE matches that of diesel, leading to higher solubility (swell) in this fuel type. Finally, the relatively low volume expansion following exposure indicates that many of the existing infrastructure plastics (excluding PTU) should be suitable for use with bio-oil.

09 BIOMASS FUELS↗

Efficient Functionalization of Polyethylene Fibers for the Uranium Extraction from Seawater through Atom Transfer Radical Polymerization

Brush-on-brush structures are proposed as one method to overcome support effects in grafted polymers. Utilizing glycidyl methacrylate (GMA) grafted on polyethylene (PE) fibers using radiation-induced graft polymerization (RIGP) provides a hydrophilic surface on the hydrophobic PE. When integrated with atom transfer radical polymerization (ATRP), the grafting of acrylonitrile (AN) and hydroxyethyl acrylate (HEA) can be controlled and manipulated more easily than with RIGP. Poly(acrylonitrile)-co-poly(hydroxyethyl acrylate) chains were grown via ATRP on PE-GMA fibers to generate an adsorbent for the extraction of uranium from seawater. The prepared adsorbents in this study demonstrated promise (159.9 g- U/kg of adsorbent) in laboratory screening tests using a high uranium concentration brine and 1.24 g-U/Kg of adsorbent in the filtered natural seawater in 21-days. The modest capacity in 21- days exceeds previous efforts to generate brush-on-brush adsorbents by ATRP while manipulating the apparent surface hydrophilicity of the trunk material (PE).

Neti, Venkata S.↗

System for determining biofuel concentration

A measurement device or system configured to measure the content of biofuels within a fuel blend. By measuring a state of a responsive material within a fuel blend, a biofuel content of the fuel blend may be measured. For example, the solubility of a responsive material to biofuel content within a fuel blend, may affect a property of the responsive material, such as shape, dimensional size, or electrical impedance, which may be measured and used as a basis for determining biofuel content.

09 BIOMASS FUELS↗

Enhancing Uranium Uptake by Amidoxime Adsorbent in Seawater: An investigation for optimum alkaline conditioning parameters

A high-surface-area polyethylene-fiber adsorbent (AF160-2) has been developed at the Oak Ridge National Laboratory (ORNL) by radiation-induced graft polymerization of acrylonitrile and itaconic acid. The grafted nitriles were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with potassium hydroxide (KOH) by varying different reaction parameters such as KOH concentration (0.2, 0.44, and 0.6 M), duration (1, 2, and 3 h), and temperature (60, 70, and 80 ºC). Adsorbent screening was then performed with simulated seawater solutions containing sodium chloride and sodium bicarbonate, at concentrations found in seawater, and uranium nitrate at a uranium concentration of ~ 7-8 ppm and pH 8. FTIR and solid state NMR indicated that a fraction of amidoxime groups was hydrolyzed to carboxylate during KOH conditioning. The uranium adsorption capacity in the simulated seawater screening solution gradually increased with conditioning time and temperature for all KOH concentrations. It was also observed that the adsorption capacity increased with an increase in concentration of KOH for all the conditioning times and temperatures. AF160-2 adsorbent samples were also tested with natural seawater using flow-through experiments to determine uranium adsorption capacity with varying KOH conditioning time and temperature. Based on uranium loading capacity values of several AF160-2 samples, it was observed that changing KOH conditioning time from 3 to 1 h at 60, 70, and 80 ºC resulted in increase of the uranium loading capacity in seawater, which did not follow the trend found in laboratory screening with stimulated solutions. Longer KOH conditioning times lead to significantly higher uptake of divalent metal ions, such as calcium and magnesium, which is a result of amidoxime conversion into less selective carboxylate. Scanning electron microscopy showed that long conditioning times may also lead to adsorbent degradation

Das, S.↗

Extracting Uranium from Seawater: Promising AI Series Adsorbents

A new series of adsorbents (AI10 through AI17) were successfully developed at ORNL by radiation induced graft polymerization (RIGP) of acrylonitrile (AN) and vinylphosphonic acid (VPA) (at different mole to mole ratios) onto high surface area polyethylene fiber, with high degrees of grafting (DOG) varying from 110 to 300%. The grafted nitrile groups were converted to amidoxime groups by reaction with 5 wt % hydroxylamine at 80 °C for 72 h. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with prescreening brine spiked with 8 ppm uranium. Uranium adsorption capacities in prescreening ranged from 171 to 187 g-U/kg-ads irrespective of percent DOG. The performance of the adsorbents with respect to uranium adsorption in natural seawater was also investigated using flow-throughcolumn testing at the Pacific Northwest National Laboratory (PNNL). Three hours of KOH conditioning led to higher uranium uptake than 1 h of conditioning. The adsorbent AI11, containing AN and VPA at the mole ratio of 3.52, emerged as the potential candidate for the highest uranium adsorption (3.35 g-U/kg-ads.) after 56 days of exposure in seawater flow-through-columns. The rate of vanadium adsorption over uranium linearly increased throughout the 56 days of exposure. The total mass of vanadium uptake was ~5 times greater than uranium after 56 days.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Extracting Uranium from Seawater: Promising AF Series Adsorbents

A new family of high-surface-area polyethylene fiber adsorbents named the AF series was recently developed at the Oak Ridge National Laboratory (ORNL). The AF series adsorbents were synthesized by radiation-induced graft polymerization of acrylonitrile and itaconic acid (at different monomer/comonomer mol ratios) onto high surface area polyethylene fibers. The degree of grafting (%DOG) of AF series adsorbents was found to be 154-354%. The grafted nitrile groups were converted to amidoxime groups by treating with hydroxylamine. The amidoximated adsorbents were then conditioned with 0.44 M KOH at 80 °C followed by screening at ORNL with sodium-based synthetic aqueous solution, spiked with 8 ppm uranium. The uranium adsorption capacity in simulated seawater screening ranged from 170 to 200 g-U/kg-ads irrespective of %DOG. A monomer/comonomer molar ratio in the range of 7.57-10.14 seemed to be optimum for highest uranium loading capacity. Subsequently, the adsorbents were also tested with natural seawater at Pacific Northwest National Laboratory (PNNL) using flow-through column experiments to determine uranium loading capacity with varying KOH conditioning times at 80 °C. The highest adsorption capacity of AF1 measured after 56 days of marine testing was demonstrated as 3.9 g-U/kg-adsorbent and 3.2 g-U/kg-adsorbent for 1 and 3 h of KOH conditioning at 80 °C, respectively. Based on capacity values of several AF1 samples, it was observed that changing KOH conditioning from 1 to 3 h at 80 °C resulted in a 22-27% decrease in uranium adsorption capacity in seawater.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Alternative Alkaline Conditioning of Amidoxime Based Adsorbent for Uranium Extraction from Seawater

Alkaline conditioning of the amidoxime based adsorbents is a significant step in the preparation of the adsorbent for uranium uptake from seawater. The effects of various alkaline conditioning parameters such as the type of alkaline reagent, reaction temperature, and reaction time were investigated with respect to uranium adsorption capacity from simulated seawater (spiked with 8 ppm uranium) and natural seawater (from Sequim Bay, WA). An adsorbent (AF1) was prepared at the Oak Ridge National Laboratory by radiation-induced graft polymerization (RIGP) with acrylonitrile and itaconic acid onto high-surface-area polyethylene fibers. For the AF1 adsorbent, sodium hydroxide emerged as a better reagent for alkaline conditioning over potassium hydroxide, which has typically been used in previous studies, because of higher uranium uptake capacity and lower cost over the other candidate alkaline reagents investigated in this study. Use of sodium hydroxide in place of potassium hydroxide is shown to result in a 21-30% decrease in the cost of uranium recovery.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Characterization and Testing of Amidoxime-Based Adsorbent Materials to Extract Uranium from Natural Seawater

Extraction of uranium (U) from seawater for use as a nuclear fuel is a significant challenge due to the low concentration of U in seawater (~3.3 ppb) and difficulties to selectively extract U from the background of major and trace elements in seawater. The Pacific Northwest National Laboratory (PNNL)’s Marine Sciences Laboratory (MSL) has been serving as a marine test site for determining performance characteristics (adsorption capacity, adsorption kinetics, and selectivity) of novel amidoxime-based polymeric adsorbents developed at Oak Ridge National Laboratory (ORNL) under natural seawater exposure conditions. This manuscript describes the performance of three formulations (38H, AF1, AI8) of amidoxime-based polymeric adsorbents produced at ORNL in MSL’s ambient seawater testing facility. The adsorbents were produced in two forms, fibrous material (40-100 mg samples) and braided material (5-10 g samples), and exposed to natural seawater using flow-through columns and recirculating flumes. All three formulations demonstrated high 56 day uranium adsorption capacity (>3 g U/kg adsorbent). The AF1 formulation had the best uranium adsorption performance, with a 56 day capacity of 3.9 g U/ kg adsorbent, a saturation capacity of 5.4 g U/kg adsorbent, and ~25 days half-saturation time. The two exposure methods, flowthrough columns and flumes, were demonstrated to produce similar performance results, providing confidence that the test methods were reliable, that scaling up from 10’s of mg quantities of exposure in flow-through columns to gram quantities in flumes produced similar results, and confirm that the manufacturing process produces a homogeneous adsorbent. Adsorption kinetics appear to be element specific, with half-saturation times ranging from minutes for the major cations in seawater, to 8-10 weeks for V and Fe. Reducing the exposure time provides a potential pathway to improve the adsorption capacity of U by reducing the V/U ratio on the adsorbent.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Effect of Biofouling on the Performance of Amidoxime-Based Polymeric Uranium Adsorbents

The Marine Science Laboratory at the Pacific Northwest National Laboratory evaluated the impact of biofouling on uranium adsorbent performance. A surface modified polyethylene adsorbent fiber provided by Oak Ridge National Laboratory, AF adsorbent, was tested either in the presence or absence of light to simulate deployment in shallow or deep marine environments. 42-day exposure tests in column and flume settings showed decreased uranium uptake by biofouling. Uranium uptake was reduced by up to 30 %, in the presence of simulated sunlight, which also increased biomass accumulation and altered the microbial community composition on the fibers. These results suggest that deployment below the photic zone would mitigate the effects of biofouling, resulting in greater yields of uranium extracted from seawater.

adsorbents↗

New Fiber Materials with Sorption Capacity at 5.0 g-U/kg Adsorbent under Marine Testing Conditions

The Fuel Resources program of the Fuel Cycle Research and Development program of the Office of Nuclear Energy (NE) has focused on assuring that nuclear fuel resources are available in the United States for a long term. An immense source of uranium is seawater, which contains an estimated amount of 4.5 billion tonnes of dissolved uranium. Extraction of the uranium resource in seawater can provide a price cap and ensure centuries of uranium supply for future nuclear energy production. NE initiated a multidisciplinary program with participants from national laboratories, universities, and research institutes to enable technical breakthroughs related to uranium recovery from seawater. The goal is to develop advanced adsorbents to make the seawater uranium recovery technology a cost competitive, viable technology. Under this program, Oak Ridge National Laboratory (ORNL) has developed several novel adsorbents, which enhanced the uranium capacity 4-5 times from the state-of-the art Japanese adsorbents. Uranium exists uniformly at a concentration of ~3.3 ppb in seawater. Because of the vast volume of the oceans, the total estimated amount of uranium in seawater is approximately 1000 times larger than its amount in terrestrial resources. However, due to the low concentration, a significant challenge remains for making the extraction of uranium from seawater a commercially viable alternative technology. The biggest challenge for this technology to overcome to efficiently reduce the extraction cost is to develop adsorbents with increased uranium adsorption capacity. Two major approaches were investigated for synthesizing novel adsorbents with enhanced uranium adsorption capacity. One method utilized conventional radiation induced graft polymerization (RIGP) to synthesize adsorbents on high-surface area trunk fibers and the other method utilized a chemical grafting technique, atom-transfer radical polymerization (ATRP). Both approaches have shown promising uranium extraction capacities: RIGP adsorbent achieved 5.00 ± 0.15 g U/kg-ads., while ATRP adsorbent achieved 6.56 ± 0.33 g U/kg-ads., after 56 days of seawater exposure. These achieved values are the highest adsorption capacities ever reported for uranium extraction from seawater. The study successfully demonstrated new fiber materials with sorption capacity at 5.0 g-U/kg adsorbent under marine testing conditions. Further optimization, investigation of other new materials as well as deepening our understanding will develop adsorbents that have even higher uranium adsorption capacity, increased selectivity, and faster kinetics.

36 MATERIALS SCIENCE↗

The Uranium from Seawater Program at the Pacific Northwest National Laboratory: Overview of Marine Testing, Adsorbent Characterization, Adsorbent Durability, Adsorbent Toxicity, and Deployment Studies

The Pacific Northwest National Laboratory’s (PNNL) Marine Science Laboratory (MSL) located along the coast of Washington State is evaluating the performance of uranium adsorption materials being developed for seawater extraction under realistic marine conditions with natural seawater. Two types of exposure systems were employed in this program: flow-through columns for testing of fixed beds of individual fibers and pellets and a recirculating water flume for testing of braided adsorbent material. Testing consists of measurements of the adsorption of uranium and other elements from seawater as a function of time, typically 42 to 56 day exposures, to determine the adsorbent capacity and adsorption rate (kinetics). Analysis of uranium and other trace elements collected by the adsorbents was conducted following strong acid digestion of the adsorbent with 50% aqua regia using either Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) or Inductively Coupled Plasma Mass Spectrometer (ICP-MS). The ORNL 38H adsorbent had a 56 day adsorption capacity of 3.30 ± 0.68 g U/ kg adsorbent (normalized to a salinity of 35 psu), a saturation adsorption capacity of 4.89 ± 0.83 g U/kg of adsorbent material (normalized to a salinity of 35 psu) and a half-saturation time of 28 ± 10 days. The AF1 adsorbent material had a 56 day adsorption capacity of 3.9 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu), a saturation capacity of 5.4 ± 0.2 g U/kg adsorbent material (normalized to a salinity of 35 psu) and a half saturation time of 23 ± 2 days. The ORNL amidoxime-based adsorbent materials are not specific for uranium, but also adsorb other elements from seawater. The major doubly charged cations in seawater (Ca and Mg) account for a majority of the cations adsorbed (61% by mass and 74% by molar percent). For the ORNL AF1 adsorbent material, U is the 4th most abundant element adsorbed by mass and 7th most abundant by molar percentage

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elution of uranium and transition metals from amidoxime-based polymer adsorbents for sequestering uranium from seawater

High-surface-area amidoxime and carboxylic acid grafted polymer adsorbents developed at Oak Ridge National Laboratory were tested for sequestering uranium in a flowing seawater flume system at the PNNL-Marine Sciences Laboratory. FTIR spectra indicate that a KOH conditioning process is necessary to remove the proton from the carboxylic acid and make the sorbent effective for sequestering uranium from seawater. The alkaline conditioning process also converts the amidoxime groups to carboxylate groups in the adsorbent. Both Na 2 CO 3 H 2 O 2 and hydrochloric acid elution methods can remove ~95% of the uranium sequestered by the adsorbent after 42 days of exposure in real seawater. The Na 2 CO 3 H 2 O 2 elution method is more selective for uranium than conventional acid elution. Iron and vanadium are the two major transition metals competing with uranium for adsorption to the amidoxime-based adsorbents in real seawater. Tiron (4,5-Dihydroxy-1,3-benzenedisulfonic acid disodium salt, 1 M) can remove iron from the adsorbent very effectively at pH around 7. The coordination between vanadium (V) and amidoxime is also discussed based on our 51V NMR data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experiments and Modeling of Uranium Adsorption in the Presence of Other Ions in Simulated Seawater

Seawater contains uranium at an average concentration of 3.3 ppb, as well as a variety of other ions at either overwhelmingly higher or similar concentrations, which complicate the recovery of uranium. This report describes an investigation of the effects of various factors such as uranium speciation and presence of salts including sodium, calcium, magnesium, and bicarbonate, as well as trace elements such as vanadium on uranium adsorption kinetics in laboratory experiments. Adsorption models are also developed to describe the experimental data of uranium extraction from seawater. Results show that the presence of calcium and magnesium significantly slows down the uranium adsorption kinetics. Vanadium can replace uranium from amidoxime-based adsorbent in the presence of sodium in the solution. Results also show that bicarbonate in the solution strongly competes with amidoxime for binding uranium, and thus slows down the uranium adsorption kinetics. Developed on the basis of the experimental findings, the model is capable of describing the effects of pH, ionic strength, temperature, and concentration of various species. The results of this work are useful in the understanding of the important factors that control the adsorbent capacity and kinetics of uranium uptake by amidoxime-based adsorbents.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Towards understanding KOH conditioning of amidoxime-based oolymer adsorbents for sequestering uranium from seawater

Conditioning of polymer fiber adsorbents grafted with amidoxime and carboxylic acid groups is necessary to make the materials hydrophilic for sequestering uranium from seawater. In this paper, spectroscopic techniques were employed to study the effectiveness of the traditional KOH conditioning method (2.5% KOH at 80⁰C) on recently developed high-surface-area amidoxime-based polymer fiber adsorbents developed at Oak Ridge National Laboratory. FTIR spectra reveal that the KOH conditioning process removes the proton from the carboxylic acids and also converts the amidoxime groups to carboxylate groups in the adsorbent. With prolonged KOH treatment (>1 hr) at 80⁰C, physical damage to the adsorbent material occurs which can lead to a significant reduction in the adsorbent's uranium adsorption capability in real seawater during extended exposure times (>21 days). The physical damage to the adsorbent can be minimized by lowering KOH conditioning temperature. For the high-surface-area amidoxime-based adsorbents, 20 min of conditioning in 2.5% KOH at 80⁰C or 1 hr of conditioning in 2.5% KOH at 60⁰C appears sufficient to achieve de-protonation of the carboxylic acid with minimal harmful effects to the adsorbent material. Lastly, the use of NaOH instead of KOH can also reduce the cost of the base treatment process required for conditioning the amidoxime-based sorbents with minimal loss of adsorption capacity (≤7%).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗