SEARCH · Search NASA
Results for “ELEMENT 114”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
±Characterization of Group V Dubnium Homologs on DGA Extraction Chromatography Resin from Nitric and Hydrofluoric Acid Matrices and Initial Investigation of Element 114 Homolog Ge
Studies of the chemical properties of superheavy elements (SHE) pose interesting challenges due to their short half-lives and low production rates. Chemical systems must have extremely fast kinetics, fast enough kinetics to be able to examine the chemical properties of interest before the SHE decays to another nuclide. To achieve chemistry on such time scales, the chemical system must also be easily automated. Most importantly however, a chemical system must be developed which provides suitable separation and kinetics before an on-line study of a SHE can be performed. Relativistic effects make studying the chemical properties of SHEs interesting due to the impact these effects could have on the SHEs chemical properties. Relativistic effects arise when the velocity of the s orbital electrons approach the speed of light. As this velocity increases, the Bohr radius of the inner electron orbitals decreases and there is an increase in the particles mass. This contraction results in a destabilization of the energy of the outer d and f electron orbitals (5f and 6d in the case of SHE), which can cause these to expand due to their increased shielding from the nuclear charge. Another relativistic effect is the spin-orbit splitting for p, d, and f orbitals into j = 1 1/2 states. This can lead most interestingly to a possible increased stability of element 114, which due to large spin-orbit splitting of the 7p orbital and the relativistically stabilized 7p 1/2 and 7s orbital gives rise to a closed shell ground state of 7s 2 7p 1/2 2 . The homologs of element 105, dubnium (Db), Ta and Nb and the pseudo-homolog Pa, are well known to hydrolyze and form both neutral and non-neutral monoatomic and polyatomic species that may cause issues with extraction from a given chemical system. Early ion-exchange and solvent-extraction studies show mixed results for the behavior of Db. Some studies show Db behaving most similar to Ta, while others show it behaving somewhere between Nb and Pa. Much more recent studies have examined the properties of Db from HNO 3 /HF matrices, and suggest Db forms complexes similar to those of Pa. Very little experimental work into the behavior of element 114 has been performed. Thermochromatography experiments of three atoms of element 114 indicate that the element 114 is at least as volatile as Hg, At, and element 112. Lead was shown to deposit on gold at temperatures about 1000 C higher than the atoms of element 114. Results indicate a substantially increased stability of element 114. No liquid phase studies of element 114 or its homologs (Pb, Sn, Ge) or pseudo-homologs (Hg, Cd) have been performed. Theoretical predictions indicate that element 114 is should have a much more stable +2 oxidation state and neutral state than Pb, which would result in element 114 being less reactive and less metallic than Pb. The relativistic effects on the 7p 1/2 electrons are predicted to cause a diagonal relationship to be introduced into the periodic table. Therefore, 114 2+ is expected to behave as if it were somewhere between Hg 2+ , Cd 2+ , and Pb 2+ . In this work two commercially available extraction chromatography resins are evaluated, one for the separation of Db homologs and pseudo?homologs from each other as well as from potential interfering elements such as Group IV Rf homologs and actinides, and the other for separation of element 114 homologs. One resin, Eichrom's DGA resin, contains a N,N,N',N'-tetra-n-octyldiglycolamide extractant, which separates analytes based on both size and charge characteristics of the solvated metal species, coated on an inert support. The DGA resin was examined for Db chemical systems, and shows a high degree of selectivity for tri-, tetra-, and hexavalent metal ions in multiple acid matrices with fast kinetics. The other resin, Eichrom's Pb resin, contains a di-t-butylcyclohexano 18-crown-6 extractant with isodecanol solvent, which separates analytes based on steric interactions between the cavity of the crown ether and electrostatic interactions between the oxygen's of the ether and cations in the mobile phase. This particular resin has been shown to have an extremely high uptake affinity for Pb, a direct homolog of element 114, and is thus a good initial extractant to examine for a potential element 114 chemical system. Figure 1.1 shows the respective extractant molecules from the DGA and Pb resins. Batch uptake experiments were conducted to examine the uptake behavior of Ta on the DGA resin. Batch uptake experiments were also conducted to examine the uptake behavior of Ge on the Pb resin. Column experiments were designed based on batch uptake experiments of Ta, Am, Pa, Np, Zr, and Nb to establish a sequential extraction of Group IV/V homologs as well as Am for potential use as a Db chemical system.
On the adsorption and reactivity of element 114, flerovium
Flerovium (Fl, element 114) is the heaviest element chemically studied so far. To date, its interaction with gold was investigated in two gas-solid chromatography experiments, which reported two different types of interaction, however, each based on the level of a few registered atoms only. Whereas noble-gas-like properties were suggested from the first experiment, the second one pointed at a volatile-metal-like character. Here, we present further experimental data on adsorption studies of Fl on silicon oxide and gold surfaces, accounting for the inhomogeneous nature of the surface, as it was used in the experiment and analyzed as part of the reported studies. We confirm that Fl is highly volatile and the least reactive member of group 14. Our experimental observations suggest that Fl exhibits lower reactivity towards Au than the volatile metal Hg, but higher reactivity than the noble gas Rn.
Production and Decay of Element 114: High Cross Sections and the New Nucleus {sup 277}Hs
The fusion-evaporation reaction {sup 244}Pu({sup 48}Ca,3-4n){sup 288,289}114 was studied at the new gas-filled recoil separator TASCA. Thirteen correlated decay chains were observed and assigned to the production and decay of {sup 288,289}114. At a compound nucleus excitation energy of E*=39.8-43.9 MeV, the 4n evaporation channel cross section was 9.8{sub -3.1}{sup +3.9} pb. At E*=36.1-39.5 MeV, that of the 3n evaporation channel was 8.0{sub -4.5}{sup +7.4} pb. In one of the 3n evaporation channel decay chains, a previously unobserved {alpha} branch in {sup 281}Ds was observed (probability to be of random origin from background: 0.1%). This {alpha} decay populated the new nucleus {sup 277}Hs, which decayed by spontaneous fission after a lifetime of 4.5 ms.
Studies of Flerovium and Element 115 Homologs with Macrocyclic Extractants
Study of the chemistry of the heaviest elements, Z ≥ 104, poses a unique challenge due to their low production cross-sections and short half-lives. Chemistry also must be studied on the one-atom-at-a-time scale, requiring automated, fast, and very efficient chemical schemes. Recent studies of the chemical behavior of copernicium (Cn, element 112) and flerovium (Fl, element 114) together with the discovery of isotopes of these elements with half-lives suitable for chemical studies have spurred a renewed interest in the development of rapid systems designed to study the chemical properties of elements with Z ≥ 114. This dissertation explores both extraction chromatography and solvent extraction as methods for development of a rapid chemical separation scheme for the homologs of flerovium (Pb, Sn, Hg) and element 115 (Bi, Sb), with the goal of developing a chemical scheme that, in the future, can be applied to on-line chemistry of both Fl and element 115. Carrier-free radionuclides, used in these studies, of the homologs of Fl and element 115 were obtained by proton activation of high-purity metal foils at the Lawrence Livermore National Laboratory (LLNL) Center for Accelerator Mass Spectrometry (CAMS): nat In(p,n) 113 Sn, nat Sn(p,n) 124 Sb, and Au(p,n) 197m,g Hg. The carrier-free activity was separated from the foils by novel separation schemes based on ion exchange and extraction chromatography techniques. Carrier-free Pb and Bi isotopes were obtained from development of a novel generator based on cation exchange chromatography using the 232 U parent to generate 212 Pb and 212 Bi. Macrocyclic extractants, specifically crown ethers and their derivatives, were chosen for these studies; crown ethers show high selectivity for metal ions. Finally. a potential chemical system for Fl was established based on the Eichrom Pb resin, and insight to an improved system based on thiacrown ethers is presented.
Conclusions from 3 years of continuous capture plant operation without exchange of the AMP/PZ-based solvent at Niederaussem – insights into solvent degradation management
A many times heard mantra of solvent degradation management in amine-based post combustion capture is “keep the solvent clean” to minimize solvent consumption. It is assumed that the amine losses would decrease by the removal of metals, degradation products, and reactive trace components which are captured from the flue gas, like NO 2 (as potentially driving components of the amine degradation besides dissolved O 2 ). However, this theoretical hypothesis – based on results from laboratory experiments typically generated with fresh amines – disregards the complexity of the solvent matrix, interaction of potential metal catalysts with degradation products and oxidizing agents, and specific chemical requirements which must be fulfilled before a degradation mechanism can proceed. Degradation of the solvent CESAR1 (aqueous solution of 3.0 molar 2-amino-2-methylpropan-1-ol (AMP) and 1.5 molar piperazine (PZ)) is investigated in a unique long-time test campaign (testing time up to now 40 months; 24/7 operation) without replacement of the solvent inventory at the capture pilot plant at the lignite-fired power plant in Niederaussem. Three solvent management strategies with different effect mechanisms are investigated and evaluated: (a) removal of only anionic compounds and trace elements (within 75 days solvent inventory treated two times) and anionic as well as cationic compounds and trace elements (114 days, inventory treated four times) from the solvent by ion exchange, (b) adsorptive removal of trace elements from the solvent by active carbon in 35% of the operating time, and (c) removal of >80% NO 2 by flue gas pretreatment with thiosulfate/sulfite solution (dosing for 2,000 h). The results of the testing program clearly show that “solvent cleanliness” is not a well-defined parameter and that results from laboratory tests, tests without fully representative industrial flue gasses, and short-term testing of monoethanolamine cannot be generalized for other solvents and industrial application. Furthermore, these results showcase that specific degradation management considering solvent, capture plant and flue gas quality is reasonable. Overshooting efforts for solvent management are contra-productive and produce unnecessary waste streams, efficiency losses and costs.
Active Correlation Technique: Status and Development
During the recent years, at the FLNR (JINR) a successful cycle of experiments has been accomplished on the synthesis of the superheavy elements with Z = 112-118 with {sup 48}Ca beam. From the viewpoint of the detection of rare decays and background suppression, this success was achieved due to the application of a new radical technique--the method of active correlations. The method employs search in a real-time mode for a pointer to a probable correlation like recoil-alpha for switching the beam off. In the case of detection in the same detector strip an additional alpha-decay event, of 'beam OFF' time interval is prolonged automatically.
Relativistic coupled cluster study of diatomic compounds of Hg, Cn, and Fl
The structure and energetics of eight diatomic heavy-atom molecules are presented. These include the species MAu, M{sub 2}, and MHg, with M standing for the Hg, Cn (element 112), and Fl (element 114) atoms. The infinite-order relativistic 2-component Hamiltonian, known to closely reproduce 4-component results at lower computational cost, is used as framework. High-accuracy treatment of correlation is achieved by using the coupled cluster scheme with single, double, and perturbative triple excitations in large converged basis sets. The calculated interatomic separation and bond energy of Hg{sub 2}, the only compound with known experimental data, are in good agreement with measurements. The binding of Fl to Au is stronger than that of Cn, predicting stronger adsorption on gold surfaces. The bond in the M{sub 2} species is strongest for Fl{sub 2}, being of chemical nature; weaker bonds appear in Cn{sub 2} and Hg{sub 2}, which are bound by van der Waals interactions, with the former bound more strongly due to the smaller van der Waals radius. The same set of calculations was also performed using the relativistic density functional theory approach, in order to test the performance of the latter for these weakly bound systems with respect to the more accurate coupled cluster calculations. It was found that for the MAu species the B3LYP functional provides better agreement with the coupled cluster results than the B88/P86 functional. However, for the M{sub 2} and the MHg molecules, B3LYP tends to underestimate the binding energies.
Sensitive search for near-symmetric and super-asymmetric fusion-fission of the superheavy element Flerovium (Z=114)
Measurements of mass and angular distributions have been made for fission-like outcomes in reactions forming isotopes of flerovium (Z=114), using 48 Ca, 50 Ti, and 54 Cr projectiles. The dominant fast quasifission process, which masks the presence of fusion-fission, has minimum yield at the most backward angles, where the sensitivity to fusion-fission is thus highest. In fitting the backward angle mass spectra, only weak evidence for a component of super-asymmetric fission was found, but a near-symmetric fission component was consistently required for the 48 Ca + 244 Pu reaction, giving upper limit to the fusion probabilities P CN of ~10 -2 , ~5 times lower than previous results. P CN for the 50 Ti reaction was lower than 48 Ca, whilst no evidence of fusion-fission was found for the 54 Cr reaction.
Studies of SHE at SHIP
The nuclear shell model predicts that the next doubly magic shell-closure beyond {sup 208}Pb is at a proton number Z = 114, 120, or 126 and at a neutron number N = 184. The outstanding aim of experimental investigations is the exploration of this region of spherical 'Super-Heavy Elements'(SHEs). Experimental methods are described, which allowed for the identification of elements produced on a cross-section level of about 1 pb. Reactions used at SHIP are based on targets of lead and uranium. The decay data reveal that for the heaviest elements, the dominant decay mode is alpha emission, not fission. Decay properties as well as reaction cross-sections are compared with results obtained at other laboratories and with results of theoretical investigations. Finally, plans are presented for the further development of the experimental setup and the application of new techniques, as for instance the precise mass measurement of the produced nuclei using ion traps. At increased sensitivity, detailed exploration of the region of spherical SHEs will start, after first steps on the island of SHEs were made in recent years.
Quantization in Classical Mechanics and Diffusion Mechanism of Alpha Decay, Cluster Radioactivity, Spontaneous Fission
Based on the Chetaev generalized theorem the Schredinger equation as the stability condition of trajectories in classical dynamics in the presence of dissipative forces is derived. In the framework of this approach the alternative model for unified description of alpha decay, spontaneous fission, cluster radioactivity and is developed. We show the possibility of the classical (without tunneling) description of radioactive decay of heavy nuclei, when the so called noise-induced transition or, in other words, the stochastic channel of radioactive decay conditioned by the Kramers diffusion mechanism is generated under certain conditions.Using the ENSDF nuclear data, we have found the parametrized solutions of the Kramers equation of the Langevin type by the Alexandrov dynamic auto-regularization method (REGN-Dubna program). These solutions describe with high-accuracy the dependences of half-life (the decay probability) of heavy radioactive nuclei on total kinetic energy of daughter decay products.Verification of the inverse problem solution in the framework of the universal Kramers description of alpha decay, spontaneous fission, cluster radioactivity, which based on the newest experimental data for alpha-decay of even-even superheavy nuclei (Z = 114, 116, 118), shows good coincidence of the experimental and theoretical dependences of half-life on alpha-decay energy.
{alpha}-decay energy formula for superheavy nuclei based on the liquid-drop model
A formula of {alpha}-decay energy for superheavy nuclei based on the method of macroscopic model plus shell corrections is proposed. The macroscopic part of this formula is derived from the Bethe-Weizsaecker binding energy formula, and the shell corrections at N=152 and N=162 are expressed by the Mexican hat wavelet functions. The parameters of this formula are obtained through fitting to 170 {alpha}-decay energies for nuclei ranging from Z=90 to Z=118 with N{>=}140. Numerical results show that 170 existing {alpha}-decay energies can be reproduced very well; the average and standard deviations between theoretical results and experimental data are 0.177 and 0.226 MeV, respectively. The {alpha}-decay energies of newly synthesized nuclei {sup 293,294}117 and their {alpha}-decay products are also reproduced very well. In addition, the {alpha}-decay energies for nuclei with Z=110-120 are predicted and compared with the results calculated by the macroscopic-microscopic model. Great differences are found for nuclei with Z{>=}116 and N{>=}176 due to the shell effects near the hypothetical doubly magic nucleus {sup 298}114{sub 184} in the macroscopic-microscopic model. Therefore, by comparing experimental {alpha}-decay energies measured in the future with the ones predicted by these two methods, one can obtain useful information about the next proton and neutron magic numbers.
Superconductivity up to 114 K in the Bi-Al-Ca-Sr-Cu-O compound system without rare-earth elements
Stable superconductivity up to 114 K has been reproducibly detected in Bi-Al-Ca-Sr-Cu-O multiphase systems without any rare-earth elements. Pressure has only a slight positive effect on T(c). These observations provide an extra material base for the study of the mechanism of high-temperature superconductivity and also the prospect of reduced material cost for future applications of superconductivity.
Electronic Structure and Gas-Phase Behaviour of the Heaviest Elements
Electronic structures and gas-phase adsorption behaviour of the heaviest elements 112, 113 and 114 and of their lighter homologs Hg, Tl and Pb is studied on the basis of ab initio Dirac-Coulomb atomic and four-component Density Functional Theory molecular and cluster calculations. The heaviest elements were shown to have low adsorption enthalpies on Teflon and should, therefore, be well transported through Teflon capillaries from the target chamber to the chemistry set up. Adsorption enthalpies of these elements on the Au(111) surface are predicted as -44.5 kJ/mol, -158.6 kJ/mol and -68.5 kJ/mol, respectively, giving the following sequence in the adsorption temperatures 113>114>112.
A very important process of nucleosynthesis in stars
When some nuclei are free from strong gravitational field, they are unstable and will become stable nuclei by competitions of following processes: (1) neutron-evaporation; (2) spontaneous fission; and (3) beta prime 3-decay. At the initial stage, (1) and (2) are important and (3) can be ignored. The qualitative results are as follows: (1) it seems that nuclei with A 100 come from the spontaneous fission and beta prime decay of neutron-evaporated nuclei with A similiar to 140-440, which can replace the r-process; (2) the super-heavy elements with Z=114--126 (A similiar to 330--360) can be formed. They can be observed in cosmic rage if they have the halftime T 10 to the 7th poweer years; (3) the peak in the rare-earth elements comes from the symmetric fission of super-heavy elements; (4) there are more neutron-rich nuclei in the fragments; and (5) the abundances of a 83 elements in cosmic rays are one order of magnitude higher than that in the solar system.
New Superheavy Element Isotopes: 242Pu(48Ca,5n)285114
The new, neutron-deficient, superheavy element isotope {sup 285}114 was produced in {sup 48}Ca irradiations of {sup 242}Pu targets at a center-of-target beam energy of 256 MeV (E* = 50 MeV). The {alpha} decay of {sup 285}114 was followed by the sequential {alpha} decay of four daughter nuclides, {sup 281}Cn, {sup 277}Ds, {sup 273}Hs, and {sup 269}Sg. {sup 265}Rf was observed to decay by spontaneous fission. The measured {alpha}-decay Q values were compared with those from a macroscopic-microscopic nuclear mass model to give insight into superheavy element shell effects. The {sup 242}Pu({sup 48}Ca,5n){sup 285}114 cross section was 0.6{sub -0.5}{sup +0.9} pb.
Toward the Discovery of New Elements: Production of Livermorium (𝑍 = 116) with 50 Ti
The 244 Pu (50 Ti ,𝑥𝑛) 294−𝑥 Lv reaction was investigated at Lawrence Berkeley National Laboratory’s 88-Inch Cyclotron. The experiment was aimed at the production of a superheavy element with 𝑍 ≥114 by irradiating an actinide target with a beam heavier than 48 Ca. Produced Lv ions were separated from the unwanted beam and nuclear reaction products using the Berkeley Gas-filled Separator and implanted into a newly commissioned focal-plane detector system. Two decay chains were observed and assigned to the decay of 290 Lv . The production cross section was measured to be 𝜎 prod = 0.44($^{+0.58}_{−0.28}$) pb at a center-of-target center-of-mass energy of 220(3) MeV. Furthermore, this represents the first published measurement of the production of a superheavy element near the “island of stability,” with a beam of 50 Ti and is an essential precursor in the pursuit of searching for new elements beyond 𝑍 =118.
Development of the Active Correlation Method: Theoretical-Methodological Aspect
The Dubna Gas-Filled Recoil Separator (DGFRS) of the Flerov Laboratory of Nuclear Reactions (FLNR), JINR, is the most advanced facility for the synthesis and study of new superheavy nuclei. In the recent years, new elements with Z = 114 to 118 (Fl, Mc, Lv, Ts, Og) have been successfully synthesized. The DGFRS detection system and a unique method of active correlations for background suppression have played a significant role in these discoveries. Theoretical-methodological aspects of further development of the active correlation method are considered, especially in view of the upcoming commissioning of the new FLNR high-intensity DC-280 cyclotron for acceleration of heavy ions and the new gas-filled recoil separator. A numerical model of the edge effects between the neighboring strips on the p – n junction side of the DSSSD detector is presented. The corresponding empirical examples are given. A more flexible real-time algorithm is considered as a possible substitute for the current version with the rigidly set parameters. Since stability of the calibration parameters is strongly required for applying the method, the radiation stability factor is also briefly considered.