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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents

At the dissolution of solid anhydrous thallium(III) trifluoromethanesulfonate, Tl(CF 3 SO 3 ) 3 , or thallium(III) trifluoroacetate, Tl(CF 3 COO) 3 , in dimethylsulfoxide (dmso) or N,N,N’,N’-tetramethylurea (tmu), intensely red-colored complexes are formed. This red thallium complex is stable for years in dmso, while it is reduced fairly rapidly to thallium(I) in tmu with a half-life time of an hour. At the dissolution of Tl(CF 3 SO 3 ) 3 in N,N-dimethylpropyleneurea (dmpu) an immediate reduction to thallium(I) takes place. A stable colorless aqueous thallium(III) solution is obtained at the dissolution in acidic water. Stable dmso solutions and solid dmso solvates of thallium(III) perchlorate, nitrate and trifluormethanesulfonate can be prepared by adding dmso to concentrated acidic aqueous thallium(III) solutions. These experimental observations conclude that the pure solids Tl(CF 3 SO 3 ) 3 and Tl(CF 3 COO) 3 play an essential role in the formation of the red-colored thallium complexes. 205 Tl NMR data show that the red thallium complex contains equal amounts of thallium(III) and thallium(I). The structure of the red thallium complex in dmso, as determined by EXAFS, has Tl–O bond distances of 2.216(3) and 2.80(2) Å, which are in very close agreement with the bond distances obtained in the pure dmso solvates of the thallium(III) and thallium(I) ions, respectively, and a Tl···Tl distance of 3.49(1) Å bridged by oxygen atoms. From the EXAFS data it is impossible to distinguish if dmso molecules and/or trifluoromethanesulfonate ions act as bridges. DFT calculations could eliminate some structures due to the irrelevant structural parameters or the energetics of the proposed reactions.

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

Thallium bromide (TIBr) semiconductors and devices with extended life apparatus, methods, and system

Various technologies pertaining to formation or treatment of a thallium bromide crystal to improve the operable lifespan of a device that incorporates the thallium bromide crystal are described herein. In exemplary embodiments, treatments including focused ion beam implantation, selective material removal, and buffer layer application are performed on a thallium bromide crystal to inhibit motion of dislocations toward a region at which an electrical contact is desirably installed. In other exemplary embodiments, a thallium bromide crystal is doped with impurities during formation that inhibit the motion of dislocations in the crystal. In still other exemplary embodiments, a thallium bromide crystal is formed by way of processes that inhibit dislocation formation during crystal growth or eliminate dislocations in an existing thallium bromide mass.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Synthesis of porphyrin triads chelated with thallium(III) for studies of ground-state hole/electron transfer

Four target all-porphyrin triads have been prepared for fundamental studies of ground-state hole/electron transfer. Each triad contains thallium(III) porphyrins as bookends, which bear mesityl groups at the three non-linking meso-positions. The central porphyrin is a free base or thallium(III) porphyrin bearing mesityl or pentafluorophenyl groups at the two non-linking meso-positions. The linker is a 4,4 ′ -diphenylethyne unit joined at the porphyrin meso-positions. The net spacer between the two bookend thallium(III) porphyrins thus consists of diphenylethyne–porphyrin–diphenylethyne and is designed as a superexchange element for through-bond hole/electron transfer. The energetics of the superexchange element are tunable given the nature of the substituents and metalation state of the central porphyrin. The synthesis entailed Sonogashira coupling of two building blocks, a free base bis(4-iodophenyl)porphyrin and a mono-ethynylporphinato thallium(III) chloride. Two benchmark porphyrins also were prepared. Absorption spectral comparisons are provided including of the all-thallium(III) monomer, dimer, and triad.

Chemistry↗
DOE OSTI2023

Development of low-loss minimal exposure technique for thallium foil fabrication

Despite its availability as a solid bead or ingot, non-isotopic thallium metal is no longer commercially produced as a foil because of its high toxicity. To conduct fundamental studies on the material, the Stable Isotope Materials and Chemistry Group (SIMC) at Oak Ridge National Laboratory (ORNL) was approached to develop a safe method to process thallium and produce 40 non-isotopic thallium foils. The commercially sourced metal was consolidated into an ingot by melting the material in a special tube furnace under a reducing atmosphere. The resulting ingot was cold rolled using a work-hardened, stainless-steel pack and oil lubricant before cutting the final foils to 2.5 × 2.5 cm2 area and thickness of 50–75 mg/cm2. The appropriate safeguards used at each step are outlined to ensure the safe and consistent production of high-quality foils. The low-loss process enables future requests for isotopic thallium and other hazardous and rare materials.

Conner, Jenny↗
DOE OSTI2020

Thallium salen fluorescent tracers

Thallium salens can be synthesized by reacting thallium alkoxide with a salen ligand. As examples of the invention, the dinuclear complexes Tl2-(salo-But) and Tl2-(saloPh-But) were synthesized by the reaction of thallium ethoxide with (H2-salo-But) or (H2-saloPh-But). These thallium salens may have applications as fluorescent tracers (or taggants) for subterranean fluid flows.

36 MATERIALS SCIENCE↗
DOE OSTI2023

A commentary on thallium radiochemistry in conjunction with OPEX23

Thallium radiochemistry was developed as a routine analytical capability at Los Alamos, dating from some of its earliest history after WWII. The first post-war compilation of radiochemical procedures published by the Radiochemistry Group J-11 is dated February 1953 as Los Alamos report LA-1566. The thallium radiochemistry procedure was authored by René J. Prestwood, and the details of the method as documented in 1953 are nearly identical to the thallium procedure contained in the most recent Collected Radiochemical and Geochemical Procedures (Fifth Edition) contained in Los Alamos report LA-1721 issued May 1990. René was a talented and well-respected member of the Radiochemistry Group. He first came to the lab in 1943 as an undergraduate student from UC Berkeley to join the Manhattan Project. After the war, René earned his PhD in Nuclear Chemistry with Art Wahl at Washington University in St. Louis. He then returned to Los Alamos as a technical staff member and retired in 1984. René passed away at the age of 92 on December 21, 2012.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2024

Synthesis of (oxo)chlorin dimers chelated with thallium(III)

Two target dimers have been prepared for fundamental studies of hole/electron transfer. Metalation with thallium(III) enables clocking of the rate of hole/electron transfer between the two macrocycles. Each dimer contains a diphenylethyne linker joining two identical hydroporphyrins (chlorin or oxochlorin). The linker is substituted at the 4,4′-positions whereas each (oxo)chlorin is joined at the 10-position. Each (oxo)chlorin is equipped with a gem-dimethyl group at the 18-position to stabilize the hydroporphyrin chromophore toward adventitious dehydrogenation and a 3,5-di-tert-butyl group at the 5-position to achieve increased solubilization in organic media. The dimers parallel a prior set of diphenylethyne-linked (oxo)chlorin constructs containing zinc-free base, zinc-zinc, and copper-copper metalation states that have been examined in studies of electronic communication. The building block (oxo)chlorins for preparing the thallium-containing dimers have been prepared in quantities of 32–404 mg, a scale up to 14-fold larger than previously. Thallation of the free base (oxo)chlorin dimers was achieved with excess TlCl 3 ⋅4H 2 O in CH 2 Cl 2 /CH 3 OH (3–4:1) upon overnight reaction at room temperature. The long-wavelength (Q[Formula: see text] absorption band of (oxo)chlorins lies between that of the zinc(II) and free base counterparts. Absorption spectral comparisons are provided of the thallium(III) and free base (oxo)chlorin monomers and dimers.

Chemistry↗
DOE OSTI2020

Indium and thallium extraction into betainium bis(trifluoromethylsulfonyl)imide ionic liquid from aqueous hydrochloric acid media

The partitioning behavior of indium and thallium ions between aqueous hydrochloric acid solutions and hydrophobic betainium bis(trifluoromethylsulfonyl)imide ionic liquid was studied using a standard liquid–liquid extraction technique. The experiments were mainly carried out by means of a radiochemical method, using 111 In and 201 Tl medical radionuclides at an ultra-trace concentration. Both mono- and trivalent thallium were utilized and the highest oxidation state (3+) was produced by adding either chlorine or bromine water to the aqueous phase prior to extraction. The metal ion transfer was optimized by varying the aqueous concentration of hydrochloric acid and by introducing zwitterionic betaine as an extracting agent into the aqueous phase. It was found that the highest D values of In(III), Tl(III) and Tl(I) in the investigated chemical systems were up to 200, 70, and 1, respectively. The influence of the addition of lithium salt, having common with the ionic liquid counterion, and the variation of mixing time on the distribution ratio of the metal ions were also studied. Finally, to understand the underlying extraction mechanism of the metal ions and to propose the predominant extracted species, mathematical models based on ion pair formation and ion exchange were developed.

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

Valence states of cyclotron-produced thallium

The unexpected behavior of thallium atoms, produced in a reaction of gold target with accelerated 3 He ions, in liquid–liquid extraction with [C n mim][NTf 2 ] ionic liquids ( n = 2, 4, 6–8, 10) was investigated. Contrary to the general expectations, a significant proportion of thallium produced in the nuclear reaction was found in a non-monovalent state upon dissolution of the KCl aerosol collector. This finding is critical for the design and evaluation of the forthcoming chemistry experiments with the superheavy element nihonium.

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

Spin‐Orbit Effects in a Thallium Borohydride Stabilized by Coordination to Bis(diisopropylamino)Cyclopropenylidene (BAC)

The reaction of Tl(OTf) with 2 equiv of bis(diisopropylamino)cyclopropenylidene (BAC) in THF results in formation of [Tl(BAC) 2 (OTf)] (1) in moderate yields. Subsequent reaction of 1 with [K][H 2 -9-BBN] ([H 2 -9-BBN] − = dihydrido 9-boratabicyclo[3.3.1]nonane) in THF results in formation of [Tl(BAC)(μ-H 2 -9-BBN)] 2 (3), also in moderate yield. Complex 3 is the first reported thallium borohydride. We attribute its thermal stability to the strong donor ability of the BAC co-ligand. Both 1 and 3 exhibit trigonal pyramidal geometries about Tl + in the solid-state, indicative of the presence of stereochemically active lone pairs. The hydride environment in 3 is calculated to exhibit a 3.9 ppm downfield shift attributed to spin-orbit effects from the adjacent Tl center.

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

Thallium-based scintillators for high-resolution gamma-ray spectroscopy: Ce 3+ - doped Tl 2 LaCl 5 and Tl 2 LaBr 5

In this paper we report on the crystallographic and scintillation properties of Tl 2 LaCl 5 :Ce 3 + and Tl 2 LaBr 5 :Ce 3 + , two novel thallium-containing high-resolution scintillators for gamma-ray spectroscopy. Crystals of Tl 2 LaCl 5 :Ce 3 + and Tl 2 LaBr 5 :Ce 3 + were grown by the Vertical Bridgman method up to 1-inch diameter and 1-inch long. Single crystals of Tl 2 LaCl 5 :Ce 3 + and Tl 2 LaBr 5 :Ce 3 + belong to the orthorhombic system with space group 62 and have a density of 5.16 and 5.98 g/cm 3 , respectively. The scintillators show high light yields of up to 68,000 photons/MeV, excellent gamma-ray energy resolution of ≤ 3% at 662 keV, a fast scintillation decay, and a proportional response over a wide range of energies from 32 keV up to 1275 keV. Density Functional Theory calculations show that the Ce 3 + energy levels are inside the bandgap despite the smaller bandgap of Tl 2 LaCl 5 and Tl 2 LaBr 5 compared to K 2 LaCl 5 and K 2 LaBr 5 . Finally, a systematic Ce 3 + concentration study was performed for Tl 2 LaCl 5 :Ce 3 + and trends observed.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2020

Effect of hydrophobic ionic liquids aqueous solubility on metal extraction from hydrochloric acid media: Mathematical modelling and trivalent thallium behavior

A mathematical model to explain cations’ solubility of both protic and aprotic ionic liquids in a wide range of hydrochloric acid solutions has been developed. The concept of this model is based on an assumption of the mineral acid extraction into the organic phase, formation of a salt there between an ionic liquid cation and chloride-anion due to ions recombination and partial salt back-extraction. The proposed approach allows estimating corresponding extraction constants. Comparison of calculated and experimentally measured solubility product constants shows that they are in good agreement. It has been determined also that the more the hydrophilicity of the ionic liquids’ cation the more hydrochloric acid is extracted. Furthermore, this model has been utilized to facilitate analysis of thallium transfer into hydrophobic ionic liquids providing insights into the mechanism of metal extraction.

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

Inelastic dark matter scattering off Thallium cannot save DAMA

We study the compatibility of the observed DAMA modulation signal with inelastic scattering of dark matter (DM) off of the 0.1% Thallium (Tl) dopant in DAMA. In this work we test whether there exist regions of parameter space where the Tl interpretation gives a good fit to the most recent data from DAMA, and whether these regions are compatible with the latest constraints from other direct detection experiments. Previously, Chang et al. in 2010, had proposed the Tl interpretation of the DAMA data, and more recently (in 2019) the DAMA/LIBRA collaboration found regions in parameter space of Tl inelastic scattering that differ by more than 10σ from a no modulation hypothesis. We have expanded upon their work by testing whether the regions of parameter space where inelastic DM-Tl scattering gives a good fit to the most recent DAMA data survive the constraints placed by the lack of a DM signal in XENON1T and CRESST-II. In addition, we have tested how these regions change with the main sources of uncertainty: the Tl quenching factor, which has never been measured directly, and the astrophysical uncertainties in the DM distribution. We conclude that inelastic DM scattering off Tl cannot explain the DAMA data in light of null results from other experiments.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Thallium-208: A Beacon of In Situ Neutron Capture Nucleosynthesis

Here, we demonstrate that the well-known 2.6 MeV gamma-ray emission line from thallium-208 could serve as a real-time indicator of astrophysical heavy element production, with both rapid (r) and intermediate (i) neutron capture processes capable of its synthesis. We consider the r process in a Galactic neutron star merger and show Tl-208 to be detectable from ~12 hours to ~ten days, and again ~1–20 years postevent. Detection of Tl-208 represents the only identified prospect for a direct signal of lead production (implying gold synthesis), arguing for the importance of future MeV telescope missions which aim to detect Galactic events but may also be able to reach some nearby galaxies in the Local Group.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Neutron Induced Nuclear Reaction Cross Sections for Radiochemistry in the Region of Thallium, Lead, and Bismuth

We have developed a set of modeled nuclear reaction cross sections for use in radiochemical detector diagnostics. Systematics for the input parameters required by the Hauser-Feshbach statistical model developed in the TALYS code system are used to calculate neutron induced nuclear reaction cross sections for targets ranging from Thallium (Z = 81) to Bismuth (Z = 83).

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Thallium Bromide Semiconductor Radiation Materials and Detectors Characterization Studies

Two overarching requirements of crucial importance for the commercial and scientific establishment of semiconductor radiation detectors are: (1) exceptionally high-purity crystals with impurity concentrations less than 1 part-per-billion and (2) single crystals that are relatively free from subgrain boundaries, secondary phases, dislocations, and other electrically-active defects. We investigated the properties of thallium bromide (TlBr) material that affect its performance with the goal of increasing the material's commercial viability for radiation detection applications. For this purpose, we used beamlines at the National Synchrotron Light Source (NSLS) at Brookhaven National Laboratory (BNL), performing Micron-scale X-ray Detector Mapping, White Beam X-ray Diffraction Topography, and Micron-scale X-ray Fluorescence. These characterization methods improve the industry's understanding of TlBr and lead to the production of improved instrumentation. In this particular study we report electro-migration measurements of positive-ion Cu, Ag, and Au impurities in TlBr detectors under electric field strengths typically used for device operation. BNL improved TlBr detectors with an electrode design that corrects the response non-uniformities caused by crystal defects. This design can achieve improved energy resolution while using typical-grade, commercial crystals with relaxed quality requirements, thus reducing the overall cost of detectors. Additional characterization will be necessary to fully understand the structure and performance of TlBr with the ultimate goal to achieve the highest energy resolution. Our findings from past work will be presented along with our recommendations for additional investigation.

36 MATERIALS SCIENCE↗