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Results for “amidoxime”

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.

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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Uranium recovery from seawater using amidoxime-based braided polymers synthesized from acrylic fibers

Global demand for nuclear energy is expected to rise in the coming decades. To meet these growing needs, new uranium resources must be explored. One of the potential alternatives to traditional uranium mining is oceanic uranium. The capture and recovery of uranium from the ocean has been under investigation for some time, with many recent studies focused on amidoxime based adsorbents. These adsorbents while able to achieve high uranium recovery capacities are, nevertheless, expensive to produce and adsorb a significant amount of hard to remove vanadium. The purpose of this study is to evaluate the adsorption performance of amidoxime based polymer braids synthesized from acrylic fibers which are designed to significantly cut polymer synthesis and conditioning costs. Adsorption experiments were performed in a recirculating raceway flume system at environmental conditions, approximately 10.8 oC, with 40-micron prefiltered seawater over 28 days for small and large sized LCW polymer braids. For both braid sizes, the adsorption of vanadium was far lower on the LCW materials than on Oak Ridge National Laboratory’s amidoxime based AF1 and AI8 small braids, with the LCW small braids outperforming both materials with respect to uranium adsorption under similar conditions. Adsorption modeling was used to simulate the performance at higher temperatures based on 20oC experiments previously performed with similar materials. Simulation results indicated that the small LCW braids would have a less significant advantage with respect to uranium adsorption over both AF1 and AI8 at 20oC and adsorb slightly less uranium than AF1 at 31oC. Vanadium adsorption by LCW small braids was less than one third of vanadium adsorption by either AF1 or AI8 for all temperatures. This behavior indicates that the LCW materials are able to achieve comparable uranium adsorption to other amidoxime adsorbents previously developed, while being cheaper to produce and adsorbing significantly less vanadium.

Wiechert, Alexander I.↗
DOE OSTI2020

Alkylamine Incorporation in Amidoxime Functionalized Polymers of Intrinsic Microporosity for Gas Capture and Separation

Amidoxime functionalized polymers of intrinsic microporosity (PIMs) are synthesized from postsynthetic functionalization of PIM‐1 with hydroxylamine and processed into chemisorbents with alkylamine incorporation. Strong interaction between functionalized PIM‐1 and primary amines is characterized in detail by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study. As‐prepared sorbents not only show the highest CO 2 uptake capacity (37.9 cm 3 g −1 at 0.15 bar and 298 K) recorded in reported PIMs, but they also demonstrate tunable, processable, and stable polymeric sorbent design, which can be nanoengineered for other gas capture and separation applications.

Miles, Ashley↗
DOE OSTI2022

Amidoxime-functionalized materials and their use in extracting metal ions from liquid solutions

A method of producing a functionalized material that extracts metal ions from solution, the method comprising: (i) providing a precursor material having nitrile groups appended to its surface; and (ii) reacting said nitrile groups with hydroxylamine or a derivative thereof in the presence of a polar aprotic solvent at a temperature of 60-80° C. for at least 1 hour, to convert at least a portion of said nitrile groups to amidoxime and imide dioxime groups, followed by reaction with a base capable of hydrolyzing any remaining nitrile groups to carboxylic acid groups; wherein said functionalized material has a higher uranium absorption capacity than a functionalized material produced under same conditions except that the nitrile groups are reacted with hydroxylamine in only a protic solvent. The invention is also directed to functionalized materials produced by the above-described method, and methods for using the functionalized material for extracting metal ions from metal-containing solutions.

Janke, Christopher J.↗
DOE OSTI2021

Strategies toward the Synthesis of Advanced Functional Sorbent Performance for Uranium Uptake from Seawater

A polymer fiber-based adsorbent (AF1) composed of acrylonitrile and itaconic acid functional groups was synthesized by a radiation-induced graft polymerization technique onto hollow-gear shaped polyethylene (PE) fibers. Investigation of the optimum reaction parameters for the conversion of grafted cyano moieties into amidoxime groups was conducted by the reaction with hydroxylamine at different temperatures and periods in a variety of aqueous and organic solvents. The 13 C CP/MAS spectra of amidoximated AF1 adsorbent fibers from water–methanol and dimethyl sulfoxide (DMSO) revealed that both the cyclic imide dioxime and open-chain amidoxime were formed through the reaction. The conversion from amidoxime to imide dioxime was found to occur slowly and gradually with the increasing reaction time. The quicker diffusion of DMSO as compared to that of water–methanol, in the grafted trunk PE fiber, resulted in faster kinetics of the amidoximation reaction. The uranium adsorption capacity of the amidoximated AF1 samples was determined after (i) 24 h contact with sodium-based brine spiked with uranium and (ii) 56 days of exposure to filtered seawater (Sequim Bay, WA, USA) in flow-through columns. Finally, the uranium extraction performance of the adsorbents after exposure to filtered seawater was consistent with the laboratory screening results, and the amidoximated AF1 samples (in DMSO at 70 °C for 3 h) exhibited the highest 56 day uranium adsorption capacity (5.04 ± 0.15 g U/kg-ads) with faster adsorption kinetics compared to the pristine AF1 adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Production of Uranium from Seawater Using a Novel Polymer Adsorbent – Process Development and Cost Analysis (Final Scientific/Technical Report SBIR Phase II)

Research in developing techniques for extracting uranium from seawater is of considerable current interest. One reason which drives scientists to develop techniques of sequestering uranium from ocean is the prediction that the land-based uranium reserves would be depleted by the end of this century based on the current production rate. Uranium exists in seawater at a very low concentration (about 3 ppb) and as highly stable uranyl tris-carbonato complexes, primarily in the form Ca 2 [UO 2 (CO 3 ) 3 ]. Because of the enormous volume of seawater, the total amount of uranium in ocean is estimated to be a thousand times greater than the land-based uranium resources. As early as 1964, the idea of extracting uranium from seawater was discussed by Davies et al. in a Nature paper. In the past decades, many different materials were tested to evaluate their ability for sequestering uranium from seawater. Among them, amidoxime and carboxylate containing polymer fiber adsorbents appear most promising because of their high uranium adsorption capacity and stability in seawater. The carboxylate groups are necessary to make the polymer adsorbent hydrophilic whereas the amidoxime groups provide strong coordination sites for uranyl ions. Moreover, according to theoretical analysis, the adsorbability of uranium may involve synergistic effects of both amidoxime and carboxyl groups in the fiber adsorbent.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Advance modification of polyacrylonitrile nanofibers for enhanced removal of hexavalent chromium from water

Hexavalent chromium [Cr(VI)] is a known carcinogenic and mutagenic heavy metal. Its level in drinking water is regulated worldwide to protect public health. This work presents a novel chemical method to modify the polyacrylonitrile (PAN) nanofibers for efficient Cr(VI) removal from water. The PAN nanofibers with an average diameter of 165 nm are produced using the electrospinning technique. Through a 2-step chemical modification process, the amidine polyacrylonitrile (APAN) nanofibers are synthesized by the conversion of nitrile groups [—C≡N] in PAN nanofibers into amidines [—C(N=NH)(NH 2 )]. The attenuated total reflectance Fourier transform (ATR-FTIR) spectroscopy revealed the successful conversion of nitrile groups into amidoximes, resulting in amidoximated polyacrylonitrile nanofibers, and subsequent conversion into amidine functional groups, forming the APAN nanofibers. Greater concentration of hydroxylamine hydrochloride, increased reaction time and temperature yielded higher conversion of nitrile groups into amidoximes to a maximum of 37%. The Cr(VI) uptake by APAN nanofibers was found as a multilayer adsorption process modeled by Freundlich isotherm. The maximum Langmuir Cr(VI) adsorption capacity for APAN nanofibers was found as 225 mg g -1 at pH = 3.0 after 4.0 h exposure duration. The regeneration study revealed the excellent reusability of APAN nanofibers after five adsorption/desorption cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1981

Bifunctional monomers having terminal oxime and cyano or amidine groups

The preparation of crosslinked 1,2,4-oxadiazole elastomers is described. The technique involves thermally condensing (1) a monomer having the formula H2N(HON)C-R-Q, wherein Q is a triazine ring-forming groups such as nitrile or amidine or a mixture of such group with amidoxime, or (2) a mixture of the same monomer with R(C(NOH)NH2)2, with R in these formulas standing for a bivalent organic radical. In the monomer charge, the overall proportions of amidoxime groups to triazine ring-forming groups varies depending on the extent of crosslinking desired in the final polymer.

Rosser, R. W.↗
NASA NTRS1981

Preparation of crosslinked 1,2,4-oxadiazole polymer

New crosslinked 1,2,4-oxadiazole elastomers were prepared by thermally condensing a monomer having the formula H2N(HON)C-R-Q, wherein Q is a triazine ring-forming group such as nitrile or amidine or a mixture of such group with amidoxime, or a mixture of said monomer with R C(NOH)NH2 sub 2 with R in these formulas standing for a bivalent organic radical. In the monomer charge, the overall proportions of amidoxime groups to triazine ring-forming groups varies depending on the extent of crosslinking desired in the final polymer.

Rosser, R. W.↗
NASA NTRS1982

Preparation of perfluorinated 1,2,4-oxadiazoles

Fluorinated alkyl or alkylether 1,2,4 oxadiazole compounds are prepared by cyclizing the corresponding alkyl or alkylether imidoyl amidoximes in vacuo or in an inert atmosphere at a temperature within the range of 40 C to 100 C. for a period of 8 to 144 hours in the presence of an acid compound which can accept ammonia to form a salt. The imidoyl amidoximes usable in this process are either polymeric or nonpolymeric. The products, when polymeric, have excellent heat, chemical and solvent resistance.

Kratzer, R. H.↗
DOE OSTI2023

Functionalized porous organic polymers as uranium nano-traps for efficient uranium extraction

Compositions are provided for efficient uranium extraction, for example from wastewater, seawater, or other water sources. The compositions can include a functionalized porous organic polymer functionalized with one or more uranium binding moieties, e.g. having a plurality of amidoxime or amidrazone groups covalently attached thereto. The compositions can include covalent organic frameworks, porous aromatic frameworks, and various porous organic polymers, especially those having a hierarchical pore size distribution over a range of pore sizes. The compositions can have functional groups such as amidoxime or an amidrazone covalently attached thereto. The hierarchical pore size distribution can be determined based upon at least 60% of the pore sizes in the range of pore sizes having a pore volume of at least 0.01 cm 3 g −1 in the pore size distribution at 77 K. Methods of making the compositions and methods of using the compositions are also provided.

Ma, Shengqian↗
DOE OSTI2022

Sequestering Rare Earth Elements and Precious Metals from Seawater Using a Highly Efficient Polymer Adsorbent Derived from Acrylic Fiber

An amidoxime and carboxylate containing polymer adsorbent derived from acrylic fiber has shown extremely high efficiencies for extracting critical materials and precious metals from seawater. Among 50 extractable elements, the lanthanides, cobalt, and palladium were ranked near the top with KD values in the order of 107, about an order of magnitude higher than that of uranium. The KD value of the lanthanides increased linearly with the atomic number indicating charge density is a factor controlling trivalent lanthanide extractability in seawater. The data given in this report provides crucial information regarding the strategies of ocean mining of critical materials and precious metals.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Evaluating the impact of functional groups on membrane‐mediated CO 2 / N 2 gas separations using a common polymer backbone

Abstract Polymeric membranes have shown tremendous promise for the separation of CO 2 from flue gas streams. However, few systematic studies have been conducted to better understand the impact that chemical functionalities have on membrane‐based gas separation performance. To address this gap, we herein describe the synthesis and gas separation performance of a series of vinyl‐addition polynorbornenes bearing various CO 2 ‐philic functional groups. To facilitate direct comparison between functional groups, each material was designed to maintain a common polymer backbone. Though the incorporation of CO 2 ‐philic moieties within a dense polymeric membrane is frequently hypothesized to enhance CO 2 solubility, and thereby increase CO 2 /N 2 selectivity, our results demonstrate that the incorporation of CO 2 ‐philic groups onto a common polymer backbone do not necessarily result in increased gas separation performance. Experimental and computational results demonstrate that the incorporation of amidoxime groups onto a polynorbornene backbone increase CO 2 /N 2 selectivity, whereas commonly employed ethereal side chains only increased permeability.

Higgins, Morgan A.↗
DOE OSTI2024

Tailoring the Interfacial Interactions of Porous Polymer Membranes to Accelerate Atomic Layer Deposition: The Latent Path to Antifouling Membranes

Atomic layer deposition (ALD) is a powerful strategy to engineer hybrid organic-inorganic membranes with emergent functionalities. The combination of atomic-level thickness control, a wide materials palette, and unprecedented conformality allows the physiochemical properties (e.g., hydrophilicity) of mesoporous polymer membranes to be precisely tuned. The nucleation of ALD material growth on polymer surfaces relies on Lewis acid-base interactions and remains an overlooked motif with tremendous potential to accelerate ALD nucleation and growth. Strategies to enhance these interactions could enable desirable properties such as antifouling behavior to be imparted on inert polymer surfaces that lack the necessary functional groups for ALD nucleation. Here, in this study, we demonstrate that the reactivity of polyacrylonitrile (PAN) membranes toward ALD metal oxide (MO) precursors with Lewis acid characteristics is enhanced by introducing strong Lewis base functional groups (amidoxime: Am) on the PAN backbone (Am-PAN). The resulting Lewis acid-base interactions accelerate the MO nucleation in Am-PAN and reduce the number of deposition cycles required to achieve hydrophilicity compared with the untreated PAN membrane. Unveiling the reaction mechanism, in situ Fourier transform infrared (FTIR) spectroscopy measurements established enhanced interaction dynamics between the ALD MO precursors and the Am-PAN membrane, unlike the PAN membrane. Spectroscopic ellipsometry and thermogravimetric analysis measurements revealed higher MO loadings in Am-PAN membranes compared to PAN membranes for the same number of ALD cycles. We found that strong Lewis acid-base interactions accelerated the ALD for a range of materials including Al 2 O 3 , TiO 2 , SnO 2 , and ZnO. More broadly, our work demonstrates that tailoring metal-precursor-polymer interactions is a powerful strategy to accelerate and modulate the ALD. We used this design strategy to fabricate Al 2 O 3 -Am-PAN hybrid membranes that showed 2-fold higher antifouling capability compared to pristine PAN membranes prepared with an equivalent number of Al 2 O 3 ALD cycles. Our approach expands the scope of design options for fouling-resistant porous hybrid inorganic-organic membranes and may ultimately reduce the operational costs of water treatment.

36 MATERIALS SCIENCE↗
DOE OSTI2024

A multifunctional technology platform for sorbent construction using polyacrylonitrile scaffolds

Polyacrylonitrile (PAN) is a synthetic polymer that shows high potential for use in a wide range of environmental remediation applications. PAN can be implemented in various ways within a batch or continuous process stream for use as a passive scaffold holding active gettering materials in place or where the PAN scaffold (e.g., beads, fiber mats, membranes) is functionalized with active chelating groups (e.g., amine, hydrazide, amidoximes, carboxyl). Application spaces covered in this review include remediation of heavy metals (e.g., Ag, As, Cd, Cr6+, Cu, Pb, Sb, and Se), high-dose fission products (e.g., 90Sr, 137Cs), radioiodine (i.e., 129I), noble gases (i.e., Xe, 85Kr), rare earths (e.g., Ce, Y), and actinides (e.g., Am, Pu, U). Methods for producing PAN composite sorbents are discussed. Options are also discussed for removing the PAN matrix following chemisorption of an active contaminant to minimize waste volumes requiring disposal.

polyacrylonitrile, composite sorbents, sulfides, a↗
DOE OSTI2023

Single polymer sorbent fibers for high performance and rapid direct air capture

Polymers of intrinsic microporosity (PIM) fibers featuring amidoxime and amine functionalities were formulated into high-performance CO 2 adsorbents. Fiber sorbents were composed of a single porous polymer component functionalized with molecular amines to increase the CO 2 capture uptake and kinetics. Here we report the highest CO 2 uptake capacity (3.3 wt% (0.8 mmol g –1 ) CO 2 at 400 ppm) among all PIM-based and single polymeric sorbents to date. Moreover, the sorbents exhibited rapid CO 2 adsorption rates (capturing 90% of its total capacity within 7 min.) and cost efficient and reproducible regeneration (at 70 °C) which are essential for reducing the cost of direct air capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗