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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 937 records · Page 52
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium

Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol -1 for the dissociation energies, D[O-(BkO + )] and D[O-(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side-on bonded η 2 -(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. Finally, the results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

A Manganese(V)–Oxo Tetraamido Macrocyclic Ligand (TAML) Cation Radical Complex: Synthesis, Characterization, and Reactivity Studies

Here, a mononuclear manganese(V)–oxo complex with tetraamido macrocyclic ligand (TAML), [Mn V (O)(TAML)] – (1), is a sluggish oxidant in oxidation reactions. Herein, a mononuclear manganese(V)–oxo TAML cation radical complex, [Mn V (O)(TAML +. )] (2), is reported. It was synthesized by reacting [Mn III (TAML)] – with 3.0 equivalents of [Ru III (bpy) 3 ] 3+ or upon addition of one–electron oxidant to 1 and then characterized thoroughly with various spectroscopic techniques along with DFT calculations. Although 1 is a sluggish oxidant, 2 is a strong oxidant capable of activating C–H bonds of hydrocarbons (i.e., hydrogen atom transfer reaction) and transferring its oxygen atom to thioanisoles and olefins (i.e., oxygen atom transfer reaction).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Synthesis of [(3,4,5‐F 3 C 6 H 2 )(4‐ n BuC 6 H 4 ) 2 C][HCB 11 Cl 11 ]: A Much More Soluble Version of the Trityl Cation with Slightly Higher Lewis Acidity

A new triarylmethyl cation (*Tr + ), designed to closely mimic Ph 3 C + in reactivity, has been prepared as a [HCB 11 Cl 11 ] − salt. *Tr + very slightly exceeds the Lewis acidity of Ph 3 C + in chloride and hydride transfer reactions, but possesses two orders of magnitude higher solubility in organic solvents of low polarity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

The electronic structure of the actinide oxides and their singly and doubly charged cations: A ligand field approach

Abstract Ligand field theory (LFT) calculations of energy levels were performed for the neutral actinide monooxides ( An O) and their singly and doubly ionized cations ( An O + and An O 2+ ) by treating the molecular electronic states as An m+ free‐ion energy levels (where An ∈ Th through Lr and m = 1, 2, 3, or 4) perturbed by the electric field of O 2− or O − . LFT parameters obtained from fits to the energy levels of ThO, ThO + , UO, and UO + were used to compute molecular energy levels for the lowest energy (maximum S c , maximum L c ) 5 f ‐core states of An 4+ , An 3+ , An 2+ , and An + for the majority of the An 4+ O 2− , An 3+ O − , An 3+ O 2− , An 2+ O − , An 2+ O 2− , and An + O − electronic configurations. Simple linear relationships enabled predictions of the dissociation energies for An O, An O + and An O 2+ (where An ∈ Bk through Lr) and ionization energies for An O and An O + (where An ∈ Bk through Lr), mainly based on recent accurate experimental data for the ionization energies of An atoms (where An ∈ Fm, Md, No, and Lr) and correlations with the energetics of the atoms and ions.

Kaledin, Leonid A.↗
DOE OSTI2022

Achieving High Stability and Performance in P2-Type Mn-Based Layered Oxides with Tetravalent Cations for Sodium-Ion Batteries

We report P2-type sodium-manganese-based layered cathodes, owing to their high capacity from both cationic and anionic redox, are a potential candidate for Na-ion batteries to replace Li-ion technology in certain applications. Still, the structure instability originates from irreversible oxygen redox at high voltage remains a challenge. Here, a high sustainability cobalt-free P2- Na 0.72 Mn 0.75 Li 0.24 X 0.01 O 2 (X= Ti/Si) cathode is developed. The outstanding capacity retention and voltage retention after 150 cycles are obtained in Na half-cells. Our finding shows Ti locates on the surface while Si diffuses to the bulk of the particles. Thus, Ti can act as protective layer that alleviate side reactions in carbonate-based electrolyte. Meanwhile, Si can regulate the local electronic structure and suppress oxygen redox activities. Notably, full-cells with hard carbon (≈300-335 Whkg -1 based on the cathode mass) deliver the capacity retention of 83% for P2- Na 0.72 Mn 0.75 Li 0.24 Si 0.01 O 2 and 66% for P2-Na 0.72 Mn 0.75 Li 0.24 Ti 0.01 O 2 after 500 cycles; this electrochemical stability is the best compared to other reported cathodes based on oxygen redox at present. The superior cycle performance also stems from the ability to inhibit microcracking and planar gliding within the particles. Altogether, this finding offers new composition towards developing high performance low-cost cathodes for Na-ion batteries and highlights the unique role of Ti/Si ions.

25 ENERGY STORAGE↗
DOE OSTI2019

Metal cation coordination and solvation studied with infrared spectroscopy in the gas phase

Transition metal cation-molecular complexes are produced in the gas phase environment of a molecular beam using laser ablation in a supersonic expansion. Complexes with carbon monoxide, carbon dioxide, water, acetylene, or benzene are produced by entraining small partial pressures of these molecules into an expansion of either argon or helium. A specially designed time-of-flight mass spectrometer is employed to analyze the ions produced and to mass select them for spectroscopy. Mass-selected ions are excited in the infrared region of the spectrum with a tunable IR optical parametric oscillator laser system to measure photodissociation spectroscopy in the 2000-4500 cm -1 region. Finally, infrared band patterns, combined with structures and spectra predicted by density functional theory, reveal the coordination and solvation interactions in these systems, and how binding to metal distorts the structures of small molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Improving the Lubricity of Extended Reach Well Drilling Equipment Using Non-Fluorescent Extreme Pressure Cationic Lubricants

In this study, non-fluorescent cationic extreme pressure lubricant JDLUB-1 was prepared to improve the lubricity for extended reach well drilling. The lubricant was mainly composed of synthetic base oil, oil-soluble and spherical nano-silica, sulfur-phosphorus-molybdenum anti-friction and anti-extreme pressure additives. The mixture was emulsified with primary emulsifier cycloalkane group condensed fatty amines and a fatty alcohol polyoxyethylene ether co-emulsifier. The fluorescence level did not exceed 4, satisfying the standard requirements. The properties including extreme pressure lubrication, temperature resistance and compatibility with conventional drilling fluid additives were evaluated. The results indicated that the extreme pressure lubricity coefficient could reach 0.0283 after addition of JDLUB-1. Meanwhile, the product was stable at high temperature of 130 °C, and compatible with common additives. The lubricity mechanism of JDLUB-1 was investigated by measuring the zeta potential, particle size distribution, adsorption, and anti-wear evaluation at extreme pressure. The results indicated that the positively charged lubricant oil droplets could be actively adsorbed onto the surface of N80 steel casing coupon. An adsorption film composed of oil soluble and spherical nano-silica and sulfur-phosphorus-molybdenum compounds was formed with a low melting point and low shear strength. During friction, the formation of molybdenum disulfide film leads to repair of the metal surface and formation of a stable sliding friction between the drill string and the wellbore with a low friction coefficient. The JDLUB-1 lubricant was successfully applied in several high-angle deviated wells and extended reach wells in Jidong oilfield (China). The results demonstrated that JDLUB-1 could effectively reduce torque and drag and show potential field application in the future.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of Viscosity and Polar Properties of Solvent on Dynamics of Photoinduced Charge Transfer in BTA-1 Cation — Derivative of Thioflavin T

It was found that the spectral and fluorescent properties of BTA-1C cation in protic and aprotic solvents differ. It was shown that for solutions in long-chain alcohols viscosity is the main factor that determines the dynamics of intramolecular charge transfer in the excited state of the BTA-1C molecule. In the case of aprotic solvents a correlation was found between the rate constant of twisted intramolecular charge transfer (TICT) during rotation of fragments of the molecule in relation to each other in the excited state and the solvent relaxation rate: k{sub TICT} ~ 1/τ{sub S}.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2018

A Novel Wastewater Treating Material: Cationic Poly Acrylamide/Diatomite Composite Flocculant

In this work, poly(methacrylatoethyl trimethyl ammonium chloride -co-acrylamide)/diatomite composite flocculant was synthesized via in situ polymerization in aqueous solution and applied in waste water treatment. The structure of composite flocculants was characterized by FT-IR, {sup 1}HNMR and XRD, TGA and viscometer. Herein, the apparent viscosity of composite flocculants was employed as comparison standard of their performance to evaluate the influence of the reaction parameters, such as monomer feeding ratio, diatomite mass fraction and polymerization temperature, etc. on their flocculation performance. And based on the above investigations, the optimum synthesis condition could be found. By comparing flocculation properties of composite flocculants with that of the conventional cationic flocculant, the dosage of composite flocculant that could make the transmittance of treated waste water exceed 95 % was only 7.5 ppm which was far lower than that of conventional flocculant (60–90 ppm). Meanwhile, the settling time was lower than 5 s which was similarly to that of conventional flocculant. Finally, the conclusion was that the composite flocculant owned higher absorption capacity and larger chain extending space than those of conventional linear flocculant due to the introduction of diatomite as backbone, which could make linear polymer chains free from entanglement and improve the flocculation capacity notably.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Novel Biocide Based on Cationic Derivative of Psyllium: Surface Modification and Antibacterial Activity

To circumvent the problems (such as volatilization, photolytic decomposition, chemical instability, easy permeability through the skin) associated with low molecular weight antimicrobial agents, our strategy employed graft copolymerization of cationic monomer with the polymeric substrate viz. psyllium husk. The surface graft concentration of quaternary ammonium ion on psyllium was optimized by measuring the extent of grafting in the microwave-induced process. The surface modification of graft copolymers was evident by different physico–chemical techniques like {sup 13}C nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), X-ray diffractometer (XRD), differential scanning calorimetry (DSC), Thermo gravimeteric analysis (TGA), and viscometric study. The synthesized water soluble product resulted good antibacterial activity against Gram positive Staphylococcus aureus and Bacillus anthracis but failed to produce any antibacterial activity against Gram negative Salmonella typhi and Escherichia coli. The reason to failure has been explained on the basis of differences in the electrokinetic property between Gram-positive and Gram-negative bacteria. Optimum minimum inhibitory concentration (MIC) for the polymeric grade which showed good biocidal effect evaluated by both zone of inhibition and absorbance is found at 1000 µg/ml.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Structure, Morphology, Cation Distribution and Magnetic Properties of Cr{sup 3+}-Substituted CoFe{sub 2}O{sub 4} Nanoparticles

The present investigations deal with the effect of trivalent chromium ions (Cr{sup 3+}) on structural and magnetic properties of nanocrystalline cobalt ferrite (CoFe{sub 2}O{sub 4}) nanoparticles. The samples of CoCr{sub x}Fe{sub 2−x}O{sub 4} (where x = 0.0 to 1.0 in step of 0.2) were successfully synthesized by citric acid-assisted sol-gel auto combustion method. Further, the prepared samples were characterized by x-ray diffraction (XRD), scanning electron microscopy (SEM), infrared spectroscopy (IR) and pulsed field hysteresis loop technique for structural, morphological and magnetic properties analysis, respectively. XRD patterns showed the formation of single-phase cubic spinel structure with broad Bragg’s peak for all the samples. The value of lattice parameter was found to be decreased with chromium substitution x. Cation distribution studies revealed that Co{sup 2+} and Fe{sup 3+} occupied both A and B sites, whereas Cr{sup 3+} ions occupied only B site. SEM analysis of the prepared samples confirmed the nanocrystalline nature of the material. The two absorption bands belonging to spinel structure were observed in IR spectra. Saturation magnetization (M{sub S}), remanence magnetization (M{sub r}) and coercivity (H{sub C}) was found to be decreased with increase in chromium substitution x.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2017

Separation of Pb, Bi and Po by cation exchange resin

In this paper, a separation of 209 Po, 207 Bi and 212 Pb using AG 50Wx8 and AG MP 50 cation exchange resins in an HCl medium was developed. A procedure in which Po(IV) elutes first in 0.2 M HCl, followed by Bi(III) in 0.4 M HCl and finally Pb(II) in 2 M HCl was established. The separation using AG 50Wx8 provides a much better elution profile than that of AG MP 50 with no overlap between the elution bands. Finally, this separation has the potential to be used as an isotope generator for producing 210 Po from 210 Pb.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2017

Cation exchange kinetics of pyridinecarboxylic acids

The sorption—desorption kinetics of nicotinic and isonicotinic acids on strong acid cationites (sulfocationite CU-2-8, sulfonated polycalixarene) were considered. The rate of the processes, following both the cation exchange mechanism H{sup +} ⇄ Cat{sup +} and the ion exchange mechanism accompanied by the chemical reaction of protonation of pyridinecarboxylic acid zwitterions, is determined by a slow diffusion of components in the polymeric phase. The interdiffusion coefficient in sulfocationite CU-2-8 for the process H{sup +} ⇄ Cat{sup +} was equal to ~1•10{sup –11} m{sup 2} s{sup –1}, in sulfonated polycalixarene the corresponding value was in the range of (1—4)•10{sup –12} m{sup 2} s{sup –1}.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Kinetic model of ethylene oxidation by p-benzoquinone in solutions of cationic palladium(II) complexes in a binary acetonitrile—water solvent

A kinetic model was developed for the reaction of ethylene oxidation to acetaldehyde by p-benzoquinone (Q) at 30 ℃ catalyzed by the cationic palladium(II) complexes in a binary acetonitrile—water solvent at a molar fraction of water of 0.67. The three-route mechanism was proposed that adequately describes all experimental dependences of the concentrations of consumed ethylene on time at various partial ethylene pressures and concentrations of palladium, perchloric acid, and Q. The time-dependent (a) palladium distribution between the intermediates and (b) ratio of the rates of steps of acetaldehyde oxidation via different routes were analyzed. The role of the Pd{sup II}, Pd{sup I}, and Pd{sup 0} complexes in the catalytic formation of olefins was discussed. The quantum chemical estimates of the composition of the coordination sphere for several intermediates and probabilities of some elementary steps in the reaction mechanism were obtained.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Novel alkyd-type coating resins produced using cationic polymerization

Novel, partially bio-based poly(vinyl ether) copolymers derived from soybean oil and cyclohexyl vinyl ether (CHVE) were produced by cationic polymerization and investigated for application as alkyd-type surface coatings. Compared to conventional alkyd resins, which are produced by high temperature melt condensation polymerization, the poly(v9nyl ether)s provide several advantages. These advantages include milder, more energy efficient polymer synthesis, elimination of issues associated with gelation during polymer synthesis, production of polymers with well-defined composition and relatively narrow molecular weight distribution, and elimination of film formation and physical property issues associated with entrained monomers, dimers, trimers, etc. The results of the studied showed that the thermal, mechanical, and physical properties of the coatings produced from these novel polymers varied considerably as a function of polymer composition and cure temperature. Overall, the results suggest a good potential for these novel copolymers to be used for coatings cured by autoxidation.

99 GENERAL AND MISCELLANEOUS↗
DOE OSTI2023

Correlation between cation order/disorder and the electrocaloric effect in the MLCCs of complex perovskite ferroelectrics

The physical properties (dielectric, ferroelectric, piezoelectric, etc.) of complex perovskite ferroelectrics depend on the degree of order/disorder and the scale of the ordered domains. In this study, the electrocaloric (EC) properties of three representative complex perovskite ferroelectrics, Pb(Mg 1/3 Nb 2/3 )O 3 -8PbTiO 3 (PMN-8PT), 1mol% Sm-doped Pb(Mg 1/3 Nb 2/3 )O 3 -8PbTiO 3 (1S-PMN-8PT) and Pb(Sc 1/2 Ta 1/2 )O 3 (PST) are evaluated. Multi-layer ceramic capacitors (MLCCs) with identical structural configurations were fabricated for these three compounds, and their EC properties were characterized by direct measurement using a thermocouple. The EC temperature change of PMN-8PT, 1S-PMN-8PT and PST MLCCs under 20 V μm –1 at room temperature were found to be 1.42 K, 1.54 K, and 3.10 K, respectively. X-ray diffraction and high-resolution transmission electron microscopy data suggests that the high EC performance of PST is related to the ordering of B-site cations (Sc 3+ and Ta 5+ ) with the ordering parameter S = 0.82 and a long coherence length of ~100 nm, such that the sample transitioned from a relaxor ferroelectric to a normal ferroelectric. Furthermore, these results provide pathway towards design of high performance EC materials required for solid state refrigeration and air-conditioning technologies.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Identification of novel Amurin-2 variants from the skin secretion of Rana amurensis, and the design of cationicity-enhanced analogues

Highlights: • Three novel Amurin-2 variants were identified from the skin secretion of Rana amurensis. • Cationic-enhanced analogues show broader antimicrobial activity spectrums. • The substitution by Lys at position 4 improves the antimicrobial selectivity on E. coli. • The cell lysis ability of Amurin-2 peptides is associated with their positive charge. Rana amurensis is important in Chinese medicine as its skin secretions contain abundant bioactive peptides. Here, we have identified the antimicrobial peptide Amurin-2 and three highly-conserved variants, Amurin-2a, Amurin-2b and Amurin-2c through a combination of molecular cloning and MS/MS fragmentation sequencing. Synthetic replicates of these peptides demonstrate potent antimicrobial activity against S. aureus, whilst some have activity against C.albicans and even resistant bacterial MRSA. Furthermore, two Lys-analogues (K{sup 4}-Amurin-2 and K{sup 11}-Amurin-2) were designed to improve the bioactive function and the antimicrobial activity of K{sup 4}-Amurin-2 against E.coli was enhanced distinctly. In addition, the two modified peptides also showed more potent activity against S. aureus, C. albicans and MRSA strains. Meanwhile, these peptides showed inhibitory effect on the cell viability of several cancer cells. As a result, these structural and functional studies of Amurin-2 variants and analogues could provide insights for future antimicrobial peptide design.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2018

Cationic lipid/DNA complexes manufactured by microfluidics and bulk self-assembly exhibit different transfection behavior

Highlights: • Transfection efficiency of lipid/DNA complexes manufactured by microfluidics is low. • Lipid/DNA complexes prepared by microfluidics have a minor impact on cell viability. • Optimized microfluidic manufacture will produce effective and not toxic lipoplexes. Recent advances in biochemical and biophysical research have been achieved through the employment of microfluidic devices. Microfluidic mixing of therapeutic agents with biomaterials yields systems with finely tuned physical-chemical properties for applications in drug and gene delivery. Here, we investigate the role of preparation technology (microfluidic mixing vs. bulk self-assembly) on the transfection efficiency (TE) and cytotoxicity of multicomponent cationic liposome/DNA complexes (lipoplexes) in live Chinese hamster ovarian (CHO) cells. Decoupling TE and cytotoxicity allowed us to combine them in a unique coherent vision. While bulk self-assembly produces highly efficient and highly toxic MC lipoplexes, microfluidics manufacture leads to less efficient, but less cytotoxic complexes. This discrepancy is ascribed to two main factors controlling lipid-mediated cell transfection, i.e. the lipoplex concentration at the cell surface and the lipoplex arrangement at the nanoscale. Further research is required to optimize microfluidic manufacturing of lipoplexes to obtain highly efficient and not cytotoxic gene delivery systems.

60 APPLIED LIFE SCIENCES↗