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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 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Charged Porous Polymers using a Solid C-O Cross-Coupling Reaction

We report a green, fast, efficient mechanochemical strategy for charged porous polymers (CPPs). A cationic CPP with basic anions and an anionic CPP with Li + cations were fabricated by solid grinding under solvent- free conditions. Compared with solution-based synthesis, mechanochemical grinding can shorten the reaction time from dozens of hours to several minutes (60– 90 min) to form polymers possessing a high molecular mass and low polydispersity. During the construction of CPPs, a Pd-catalyzed solid polycondensation based on unactivated organic linkers was introduced. In particular, CPPs with basic phenolic or proline anions showed good activity and stability in SO 2 capture, and Li + -functionalized CPPs can be post-modified to CPPs with other metal ions by ion exchange, highlighting the tailorable feature of ionic-modified CPPs.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Purification and preparation of graphite oxide from natural graphite

Graphite oxide has attracted much interest as a possible route for preparation of natural graphite in the large-scale production and manipulation of graphene as a material with extraordinary electronic properties. Graphite oxide was prepared by modified Hummers method from purified natural graphite sample from West Kalimantan. We demonstrated that natural graphite is well-purified by acid leaching method. The purified graphite was proceed for intercalating process by modifying Hummers method. The modification is on the reaction time and temperature of the intercalation process. The materials used in the intercalating process are H{sub 2}SO{sub 4} and KMNO{sub 4}. The purified natural graphite is analyzed by carbon content based on Loss on Ignition test. The thermo gravimetricanalysis and the Fouriertransform infrared spectroscopy are performed to investigate the oxidation results of the obtained GO which is indicated by the existence of functional groups. In addition, the X-ray diffraction and energy dispersive X-ray spectroscopy are also applied to characterize respectively for the crystal structure and elemental analysis. The results confirmed that natural graphite samples with 68% carbon content was purified into 97.68 % carbon content. While the intercalation process formed a formation of functional groups in the obtained GO. The results show that the temperature and reaction times have improved the efficiency of the oxidation process. It is concluded that these method could be considered as an important route for large-scale production of graphene.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

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↗
DOE OSTI2018

A facile recovery process for cathodes from spent lithium iron phosphate batteries by using oxalic acid

A simplistic and novel leaching process is developed to dispose spent lithium iron phosphate (LiFePO 4 ) batteries. In this paper, oxalic acid is selected as a leaching reagent to recover lithium as a resource and remove phosphorus from LiFePO 4 batteries, benefiting from its low natural effects. The physical properties of spent cathode materials (before leaching) and residues (after leaching) are identified by X-ray diffraction (XRD) and scanning electronic microscopy (SEM) with energy dispersive X-ray spectroscopy (EDS). The total amounts of Li and Fe are analyzed by inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The process occurs under conditions of a 0.3 mol·L -1 oxalic acid concentration, a temperature of 80°C, a reaction time of 60 min and a solid/liquid ratio of 60 g· L -1 . It can effectively precipitate ~92% ferrum in terms of FeC 2 O 4 ·2H 2 O from LiFePO 4 , with the leaching efficiency of Li achieving up to 98%. This method demonstrates a new strategy for dealing with spent lithium iron phosphate batteries with a low cost and low environmental impact.

25 ENERGY STORAGE↗
DOE OSTI2021

Minimizing Oxygen Permeability in Chitin/Cellulose Nanomaterial Coatings by Tuning Chitin Deacetylation

The demand for packaging materials with low gas permeabilities is increasing, but commonly used petroleum-derived single-use plastics are not renewable, biodegradable, or easy to recycle. Nanomaterials composed of chitin and cellulose, which are abundant in nature, have high crystallinities and low oxygen permeabilities (OP), providing a viable alternative. In this work, we explore how deacetylation conditions of crab shell chitin can be used to tune the charge and size of resulting chitin nanowhiskers (ChNWs) and the resulting OP of layered film structures. Three deacetylation factors, the concentration of sodium hydroxide (%NaOH), temperature (T), and reaction time, were explored using a three-factor three-level Taguchi design with an orthogonal array. Furthermore, the resulting ChNW suspensions were sequentially spray-coated with suspensions of cellulose nanocrystals (CNCs) onto cellulose acetate (CA) films to form a multilayer structure. We show that ChNWs prepared under more aggressive deacetylation conditions inside the original orthogonal array (higher %NaOH, T, and time) had shorter lengths but the surface charge was significantly influenced only by more aggressive deacetylation outside of the original design conditions. With only ~10% decrease in the ultimate tensile strength and no significant loss in failure strain, the ChNW-CNC coating resulted in ~20% decrease in WVTR in comparison to uncoated CA films. The optimization of process conditions resulted in CA-ChNW-CNC films with a 91-99% decrease in OP (132-16.7 cm 3 ∙μm/m 2 /day/kPa versus 1553 cm3∙μm/m2/day/kPa for uncoated CA).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Enhancement of photocatalytic properties of Bi{sub 2}WO{sub 6} nanoparticles by Pt deposition

Graphical abstract: - Highlights: • Pt/Bi{sub 2}WO{sub 6} was used for photocatalytic degradation of methyl orange dye. • Photocatalytic degradation was dependent on wt% of Pt reaction time, and weight of catalyst. • Kinetic study revealed that the photocatalytic degradation of methyl orange dye followed the first order. • Catalyst re-use revealed the present photocatalyst remain effective and active after five cycles. - Abstract: Bi{sub 2}WO{sub 6} nanoparticles were prepared using a hydrothermal method, and Pt was immobilized on the surface of Bi{sub 2}WO{sub 6} via a photo-assisted deposition (PAD) method. The samples produced were characterized using X-ray diffraction, ultraviolet and visible spectroscopy, photoluminescence emission spectra, transmission electron microscopy, extended X-ray absorption fine structure, and surface area measurements. Furthermore, the catalytic performance of the Bi{sub 2}WO{sub 6} and Pt/Bi{sub 2}WO{sub 6} samples was examined in the degradation of methyl orange dye (MO) under visible light. The extended X-ray absorption fine structure (EXAFS) results, which showed the presence of peaks assigned to the Pt–Pt at approximately 2.50 Å, indicate the formation of nanoscale Pt features. The UV–vis spectral analysis detected a red shift after loading the Pt into the Bi{sub 2}WO{sub 6}. The maximum degradation efficiency achieved was 100% with 0.3 Pt/Bi{sub 2}WO{sub 6} as the photocatalyst after a 30-min reaction time. The catalyst could be reused without any loss in activity for the first five cycles.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Physiochemical Characterization of Lignocellulosic Biomass Dissolution by Flowthrough Pretreatment

Comprehensive understanding of biomass solubilization chemistry in aqueous pretreatment such as water-only and dilute acid flowthrough pretreatment is of fundamental importance to achieve the goal of valorizing biomass to fermentable sugars and lignin for biofuels production. In this study, poplar wood was flowthrough pretreated by water-only or 0.05% (w/w) sulfuric acid at different temperatures (220-270 °C), flow rate (25 mL/min), and reaction times (8-90 min), resulting in significant disruption of the lignocellulosic biomass. Ion chromatography (IC), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) analysis, and solid state cross-polarization/magic angle spinning (CP/MAS) 13C nuclear magnetic resonance (NMR) spectroscopy were applied to characterize the pretreated biomass whole slurries in order to reveal depolymerization as well as solubilization mechanism and identify unique dissolution structural features during these pretreatments. Results showed temperature-dependent cellulose decrystallization in flowthrough pretreatment. Crystalline cellulose was completely disrupted, and mostly converted to amorphous cellulose and oligomers by water-only operation at 270 °C for 10 min and by 0.05 wt % H2SO4 flowthrough pretreatment at 220 °C for 12 min. Flowthrough pretreatment with 0.05% (w/w) H2SO4 led to a greater disruption of structures in pretreated poplar at a lower temperature compared to water-only pretreatment.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2016

Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acids (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated an improved viscosity index and reduced friction coefficient, validating the basic approach.

Robinson, Joshua W.↗
DOE OSTI2018

Uranium speciation in acid waste-weathered sediments: The role of aging and phosphate amendments

Uranium speciation and lability are strongly coupled to mineral transformations in silicate sediments, particularly for sediments subjected to weathering in acidic, high-level radioactive waste, as occurred at the Department of Energy's Hanford (WA) site. In this study, uncontaminated Hanford sediments were reacted for 365 days with acidic (pH 3), uranium-bearing waste solutions, with and without phosphate in batch experiments, prior to detailed characterizations using electron microscopy, x-ray diffraction and x-ray absorption spectroscopy. In PO(4)(-)reactant free systems, uranium speciation was controlled initially by precipitation of compreignacite [K-2(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-and becquerelite [Ca(UO2)(6)O-4(OH)(6)center dot 8H(2)O]-like species. Subsequent further removal of uranium coincided with that of Si and accumulation of boltwoodite, [(K, Na)(UO2)(2)O-4(HSiO4)(2)center dot 0.5(H2O)]-like species of uranium at 180 and 365 days. When present, PO4 exerted a direct and strong control over U speciation. The detection of meta-ankoleite, [K-2(UO2)(2)O-4(PO4)(2)center dot 6H(2)O] at all reaction times when U was present emphasizes the importance of dissolved phosphate as a control on U speciation. Here, meta-ankoleite appears well crystallized and when it occurs as the principal product of sediment weathering, its low solubility is expected to limit dissolved U(VI) concentrations in groundwater. Although boltwoodite solubility is also low, it is formed more slowly (and only when PO4 is absent), after initial precipitation of more soluble, less crystalline uranyl hydroxides. In the context of Hanford crib waste our results suggest that with PO4 present, nearly all uranium would have precipitated in the upper soil.

Perdrial, Nicolas↗
DOE OSTI2018

Towards Synthesis, Characterization and Properties of Smart Material Based on Chitosan Using Mn-IV Itaconic Acid as a Novel Redox Pair

The precipitation technique of Mn-IV/itaconic acid redox pair was chosen for grafting meth acrylic acid onto chitosan. This was done to maximize the graft yield and minimize the homopolymer formation to lower extent in addition to prepare water soluble chitosan instead of non-eco friendly acid soluble one. Evidence of grafting was confirmed instrumentally by (FTIR, SEM, and TGA), titrimetrically using carboxyl content and gravimetrically using dry weight method. The mechanism of grafting and factors affected grafting reaction were studied in details, and the optimum reaction conditions were obtained at [chitosan] 2 g, [MnO{sub 2}] 25.9 mmol/100 g sample, [itaconic acid],100 mmol/L, [MAA] 50% bows,[liquor ratio], 25, reaction time, 2 h, and [reaction temperature], 65 °C. It is also seen from the obtained results that, the resultant copolymer showed the following findings: (a) only nitric acid solutions are proved to be a superior solvent for the grafted product; (b) superabsorbent towards water (197 g H{sub 2}O/g polymer) and saline absorbency (60 g saline solution/g polymer) after cross-linked with epichlorohydrin, (c) higher water solubility (21%) at 48% graft yield and (d) 73.5% copper ion removal in comparison with 41% for chitosan.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Novel synthesis of manganese and vanadium mixed oxide (V{sub 2}O{sub 5}/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V{sub 2}O{sub 5}/OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V{sub 2}O{sub 5}/OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V{sub 2}O{sub 5}/K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V{sub 2}O{sub 5}/K-OMS-2 catalyst. • V{sub 2}O{sub 5}/K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidation using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V{sub 2}O{sub 5}/K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V{sub 2}O{sub 5} species. Oxidation of various alcohols was studied in the liquid phase over the V{sub 2}O{sub 5}/K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H{sub 2}O{sub 2} as the oxidant. Activity of the V{sub 2}O{sub 5}/K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V{sub 2}O{sub 5}. The kinetic of benzyl alcohol oxidation using excess TBHP over V{sub 2}O{sub 5}/K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Development of sterically hindered siloxide-functionalized polyoxotungstates for the complexation of 5d-metals

In this study, we extend the family of organosilyl-functionalized trivacant Keggin polyoxotungstates, [PW 9 O 34 (RSiOH) 3 ] 3− (R = n Pr, i Pr, t Bu), through the introduction of bulky aryl and aliphatic silanol substituents, namely phenyl, cyclohexyl and biphenyl. This work was performed in order to study the impact of these large functional groups on the accessibility of the well-defined tridentate coordination site. Coordination of hafnium to these type II hybrid polyoxotungstates was conducted in order to study the ability of the bulkier ligand pockets to support larger cations in comparison to those previously reported (e.g. Ti 4+ , V 3+ , V 5+ , Ge 4+ ). Increased steric hindrance around the coordination site from the biphenyl groups resulted in much longer reaction times for the complexation reaction compared to the other functional groups used, but the impact of our design toward stabilizing reactive species proved limited, as all complexes easily undergo hydrolysis of the Hf-O t Bu bond in the presence of water. As a result, electrochemical investigations of the ligands and hafnium complexes reveal that the redox events centered on the polyoxotungstate core can be tuned by varying the substituents on the silyl fragment, and exhibit a cathodic shift after coordination of the redox inactive tetravalent cation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Synthesis of mesoporous silica using a mineral silica source

Abstract Mesoporous silica has been applied in catalysis, separations, and drug delivery. It has generally been made using organosilicon precursors such as tetraethyl orthosilicate. For sustainability, it is necessary to find readily accessible mineral sources for making mesoporous silica. In this work, we demonstrate the successful synthesis of mesoporous silica with 10 nm average pore size using the mineral forsterite (Mg 2 SiO 4 ) as a silica source, providing a potentially cheaper and more Earth‐friendly route to making technologically important porous silica materials. Pure forsterite was synthesized by a solid‐state chemistry route at 1000°C and underwent dissolution–reprecipitation in aqueous hydrochloric acid containing the soft template surfactant, Pluronic P123. Variations of initial reaction pH (−0.2 to 0.6), reaction time (12–24 h), reaction temperature (50 to 90°C), and silica precursor (forsterite and fumed silica) were performed. The mesoporous silica aged at 70°C for 24 h had the highest porosity, with a surface area of 735 m 2 /g and a pore volume of 1.4 ml/g, comparable to mesoporous silica made using conventional starting materials. This novel geomimetic synthesis route supports the possibility of analogous formation of structured (mesoporous or zeolitic) silica in nature under abiotic or prebiotic conditions.

Materials Science↗
DOE OSTI2015

Securing Single Points of Compromise (SPoC)

Securing the Single Points of Compromise that provide central services to the institution’s environment is paramount to success when trying to protect the business. (Fisk, 2014) Time Based Security mandates protection (erecting and ensuring effective controls) that last longer than the time to detect and react to a compromise. When enterprise protections fail, providing additional layered controls for these central services provides more time to detect and react. While guidance is readily available for securing the individual critical asset, protecting these assets as a group is not often discussed. Using best business practices to protect these resources as individual assets while leveraging holistic defenses for the group increases the opportunity to maximize protection time, allowing detection and reaction time for the SPoCs that is commensurate with the inherent risk of these centralized services.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

A Novel Dynamic Polymer Synthesis via Chlorinated Solvent Quenched Depolymerization

Dynamic polymers with both physical interactions and dynamic covalent bonds exhibit superior performance while achieving such dry polymers in an efficient manner remains a challenge. Herein, we report a novel organic solvent quenched polymer synthesis using a natural molecule, i.e., thioctic acid (TA), which has both dynamic disulfide bond and carboxylic acid. The effects of the solvent types and concentrations along with reaction times on the proposed reaction have been thoroughly explored for polymer synthesis. Solid-state proton nuclear magnetic resonance ( 1 H NMR) and first-principles simulations are carried out to investigate the reaction mechanism. It shows that the chlorinated solvent can efficiently stabilize and mediate the depolymerization of poly(TA) which is more kinetically favorable upon lowering the temperature. Attributed to the numerous dynamic covalent disulfide bonds and noncovalent hydrogen bonding, the obtained poly(TA) shows high extensibility, self-healable and re-processable properties. It can also be employed as an efficient adhesive even on a Teflon surface and 3D printed using the fused deposition modeling (FDM) technique. This new polymer synthesis approach on using organic solvents as catalysts along with the unique reaction mechanism provides a new pathway for efficient polymer synthesis, especially for those multi-functional dynamic polymers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2004

PETI-298 Prepared by Microwave Synthesis: Neat Resin and Composite Properties

PETI-298 is a high temperature/high performance matrix resin that is processable into composites by resin transfer molding (RTM), resin infusion and vacuum assisted RTM techniques. It is typically synthesized in a polar aprotic solvent from the reaction of an aromatic anhydride and a combination of diamines and endcapped with phenylethynylphthalic anhydride. Microwave synthesis of PETI-298 was investigated as a means to eliminate solvent and decrease reaction time. The monomers were manually mixed and placed in a microwave oven for various times to determine optimum reaction conditions. The synthetic process was subsequently scaled-up to 330g. Three batches were synthesized and combined to give 1 kg of material that was characterized for thermal and rheological properties and compared to PETI-298 prepared by the classic solution based synthetic method. The microwave synthesized PETI-298 was subsequently used to fabricate flat laminates on T650 carbon fabric by RTM. The composite panels were analyzed and mechanical properties determined and compared with those fabricated from PETI-298 prepared by the classic solution method. The microwave synthesis process and characterization of neat resin and carbon fiber reinforced composites fabricated by RTM will be presented. KEY WORDS: Resin Transfer Molding, High Temperature Polymers, Phenylethynyl Terminated Imides, Microwave Synthesis

Smith, Joseph G.↗