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Fire extinguishant composition comprising a mixture of a finely divided aluminum compound and alkali metal, stannous or plumbous halide is provided. Aluminum compound may be aluminum hydroxide, alumina or boehmite but preferably it is an alkali metal dawsonite. The metal halide may be an alkali metal, e.g. potassium iodide, bromide or chloride or stannous or plumbous iodide, bromide or chloride. Potassium iodide is preferred.
Bolstered by recent calculations of exact functional-driven errors (FEs) and density-driven errors (DEs) of semilocal density functionals in the water dimer binding energy , we investigate approximate FEs and DEs in neutral water clusters containing up to 20 monomers, charged water clusters, and alkali- and halide-water clusters. Our proxy for the exact density is r 2 SCAN 50, a 50% global hybrid of exact exchange with r 2 SCAN, which may be less correct than r 2 SCAN for the compact water monomer but importantly more correct for long-range electron transfers in the noncompact water clusters. We show that SCAN makes substantially larger FEs for neutral water clusters than r 2 SCAN, while both make essentially the same DEs. Unlike the case for barrier heights, these FEs are small in a relative sense and become large in an absolute sense only due to an increase in cluster size. SCAN@HF, short for SCAN evaluated on the Hartree–Fock (HF) density, produces a cancellation of errors that makes it chemically accurate for predicting the absolute binding energies of water clusters. Likewise, adding a long-range dispersion correction to r 2 SCAN@HF, as in the composite method HF-r 2 SCAN-DC4, makes its FE more negative than in r 2 SCAN@HF, permitting a near-perfect cancellation of FE and DE. r 2 SCAN by itself (and even more so, r 2 SCAN evaluated on the r 2 SCAN 50 density), is almost perfect for the energy differences between water hexamers, and thus probably also for liquid water away from the boiling point. Thus, the accuracy of composite methods like SCAN@HF and HF-r 2 SCAN-DC4 is not due to the HF density being closer to the exact density, but to a compensation of errors from its greater degree of localization. We also give an argument for the approximate reliability of this unconventional error cancellation for diverse molecular properties. Lastly, we confirm this unconventional error cancellation for the SCAN description of the water trimer via Kohn–Sham inversion of the CCSD(T) density.
Defects in two-dimensional transition metal dichalcogenides (TMDCs) broadly affect their optical and electronic properties. Directly capturing the ultrafast processes of exciton trapping and defect-bound exciton formation is crucial for understanding and advancing defect-mediated optoelectronics and quantum technologies. However, the weak transient optical absorption of defect-bound excitons has limited their experimental observation to date. Here, we report the direct observation of the ultrafast dynamics of defect-bound excitons in monolayer WS 2 crystals with a high density of monosulfur vacancies (V S ) and W-site defect complexes (S W V S ) resulting from synthesis by alkali metal halide-assisted chemical vapor deposition. The dynamics of excitons bound to these defects, along with their coherent interactions with free excitons, are elucidated using ultrafast optical spectroscopy. Using above band-edge photoexcitation, we find that both free and defect-bound excitons simultaneously form within 300 fs from hot carrier relaxation. The defect-bound excitons exhibit shorter lifetimes than free excitons, leading to a population difference of the corresponding excitonic states and free exciton trapping within a 1–100 ps window. Band-edge photoexcitation of free and defect-bound exciton states reveals ultrafast interconversion within ∼150 fs (comparable to our temporal resolution), indicating possible coherent coupling between these states. We further demonstrate efficient up-conversion of defect-bound excitons to free excitons with photon energies up to ∼300 meV below the free exciton resonance. In conclusion, these findings provide insights into the ultrafast dynamics of defect-bound excitons in TMDCs and their coupling with free excitons, which are relevant to defect-engineered optoelectronic, quantum photonic, and valleytronic applications.
The results of the most extensive set to date of thermodynamic calculations on the equilibrium chemistry of several hundred compounds of the elements Na, K, F, Cl, Br, and P in a solar composition system are reported. Two extreme models of accretion are investigated. In one extreme complete chemical equilibrium between condensates and gases is maintained because the time scale for accretion is long compared to the time scale for cooling or dissipation of the nebula. Condensates formed in this homogeneous accretion model include several phases such as whitlockite, alkali feldspars, and apatite minerals which are found in chondrites. In the other extreme complete isolation of newly formed condensates from prior condensates and gases occurs due to a time scale for accretion that is short relative to the time required for nebular cooling or dissipation. The condensates produced in this heterogeneous accretion model include alkali sulfides, ammonium halides, and ammonium phosphates. None of these phases are found in chondrites. Available observations of the Na, K, F, Cl, Br, and P elemental abundances in the terrestrial planets are found to be compatible with the predictions of the homogeneous accretion model.
A method of forming ligated nanoparticles of the formula Y(Z).sub.x where Y is a nanoparticle selected from the group consisting of elemental metals having atomic numbers ranging from 21-34, 39-52, 57-83 and 89-102, all inclusive, the halides, oxides and sulfides of such metals, and the alkali metal and alkaline earth metal halides, and Z represents ligand moieties such as the alkyl thiols. In the method, a first colloidal dispersion is formed made up of nanoparticles solvated in a molar excess of a first solvent (preferably a ketone such as acetone), a second solvent different than the first solvent (preferably an organic aryl solvent such as toluene) and a quantity of ligand moieties; the first solvent is then removed under vacuum and the ligand moieties ligate to the nanoparticles to give a second colloidal dispersion of the ligated nanoparticles solvated in the second solvent. If substantially monodispersed nanoparticles are desired, the second dispersion is subjected to a digestive ripening process. Upon drying, the ligated nanoparticles may form a three-dimensional superlattice structure.
To enable thermal behavior prediction and design optimization of molten salt reactors, thermal conductivity of molten salts must be characterized in terms of salt composition and temperature. Current theoretical models fail to provide consistent approximations for all halide mixtures, particularly actinide-bearing melts. This study aims to link the short-range order structure of molten salts to the mean free path of energy carriers through a simple structural coherence model informed by the partial pair distribution function. The proposed method is used to predict the thermal conductivity of 33 alkali and alkaline earth halide salts. Predictions approximate experimental measurements with a mean absolute error of 15.7% for dissociating, complexing, and actinide salts, including unary LiCl, NaCl, and MgCl 2 as well as mixtures LiF–NaF–KF (FLiNaK), LiF–BeF 2 (FLiBe), and NaCl–UCl 3 . The work provides evidence for the validity of energy carrier descriptions of molecular-level heat transfer in molten salts, with implications for improved theories of liquid energy transport in general.
This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion-water and ion-ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range. This motivates an environment-dependent atomic polarizability parameter that depends on the strength of the local electric field experienced by the ions to account for strong damping, with anisotropy introduced by atomic multipoles. The resulting CMM model for ions provides accurate dimer surfaces and three-body polarization and charge transfer compared to EDA, and shows excellent performance on various ion benchmarks including vibrational frequencies and cluster geometries.
Proposed thermal-energy-storage system based on mixture of alkali metal and one of its halide salts; metal and salt form slurry of two immiscible melts. Use of slurry expected to prevent incrustations of solidified salts on heat-transfer surfaces that occur where salts alone used. Since incrustations impede heat transfer, system performance improved. In system, charging heat-exchanger surface immersed in lower liquid, rich in halide-salt, phase-charge material. Discharging heat exchanger surface immersed in upper liquid, rich in alkali metal.
Degradation of halide perovskites under a humid atmosphere is the major challenge preventing widespread commercial deployment of this material class. Here it is shown that strain engineering via alkali metal chloride treatment at the FAPbI 3 /SnO 2 interface effectively improves moisture-related stability. CsCl and KCl treatments reduce microstrain at the perovskite surface and slow the α- to δ-phase transformation. Alkali metal treatments with LiCl, NaCl, and RbCl led to an increase in microstrain and faster degradation. The compressive strain at the perovskite surface was the smallest for CsCl and was linked to improved stability. First-principles density functional theory calculations confirm the preferential formation of alkali defects at interstitial positions at the perovskite surface. Particularly CsCl and KCl treatments lead to a release of compressive strain at the perovskite surface and local structural distortions that may favor passivation of surface defects. In contrast, the room-temperature dynamics of Li interstitials result in an overall expansion of lattice volume, which may be linked to more facile lattice degradation.
The molecular velocity of sound was calculated according to Rao's formula and the temperature and concentration dependences of this value were studied in aqueous solutions of alkali and alkaline-earth halides. Study of relative association brought to light characteristic effects of ions. The variation of the relative association can be explained by a breaking of hydrogen bonds by ions and thermal agitation.
Mixtures of alkali metal dawsonite and metal halide show superior performance. In tests of new dry powder fire extinguishants, mixtures of potassium dawsonite with either stannous iodide or potassium iodide found effective for extinguishing jet-fuel fires on hot metal surfaces (up to 900 degrees C). Mixtures performed more effectively than either compound alone.
Process developed to make polyorganoborosilane polymers. Precursor polymers prepared by using alkali metal to couple boron halide with organohalosilane. In representative application, polymer drawn into fibers, then pyrolyzed to produce ceramic cloth. Ceramics exhibit high thermo-oxidative stability.
Only a handful of high-halide salt waste forms have been demonstrated for vitrification-based immobilization strategies for halide-salt nuclear waste streams (e.g., pyroprocessing wastes, molten salt reactor wastes) and they all have low waste loading potential and most have low chemical durabilities for high-alkali streams. An alternative approach to direct salt immobilization is salt partitioning prior to waste form fabrication and one option for partitioning is halide removal (called dehalogenation). Removing the halogen fraction through dehalogenation can significantly reduce the waste volume required for disposal in the primary waste form. Furthermore, when dehalogenation is performed using organic acids, the dehalogenation reagent can decompose during high-temperature vitrification, reducing waste loading limitations in the waste form. In the current work, different organic acids (i.e., oxalic, formic, acetic, oxamic, and citric) were evaluated for dehalogenation efficiency of a simple chloride salt simulant (7.19% LaCl 3 , 53.77% LiCl, and 39.04% KCl, by mole) and a more complex chloride salt simulant called ERV3 (electrorefiner version 3) at 150 °C–300 °C and using H + /Cl – molar ratios of 1:1, 2:1, and 3:1. Additionally, a borosilicate glass waste form called TARS (or the average of refined specifications) was formulated, produced, and characterized for dehalogenated ERV3.
Thermochemical processes which lead to the production of hydrogen and oxygen from water without the consumption of any other material have a number of advantages when compared to other processes such as water electrolysis. It is possible to operate a sequence of chemical steps with net work requirements equal to zero at temperatures well below the temperature required for water dissociation in a single step. Various types of procedures are discussed, giving attention to halide processes, reverse Deacon processes, iron oxide and carbon oxide processes, and metal and alkali metal processes. Economical questions are also considered.
The following facts were uncovered in comparing the basaltic surface rocks of the moon with terrestrial tholeiitic basalts and ordinary chondrites: (1) there is an excess of the so-called refractory chemical elements, including the group of truly refractory elements, the rare earths, U, and Th, in comparison with their content in primitive terrestrial basalts and chondrites; (2) the so-called siderophilic elements have lower contents in the lunar surface rocks than in terrestrial rocks; (3) the low alkali content (Na, K, Rb) in lunar rocks is established; (4) there is a low content of H2O and the ordinary gases CO2, halides, etc.; (5) the low content of metals with high vapor pressure, (In, Tl, etc.) has been established. It is proposed that U and Th were carried from the internal areas to the peripheral rocks of the moon during magmatic activity, i.e., up to 3 billion years ago. This redistribution of U and Th lead to their concentration in surface layers of the moon, and the heat which they generated was lost into surrounding space. The conclusion is then reached that in order to understand processes on the moon, the chondritic model cannot be used.
Actinide complexes containing the simplest borohydrides (BH 4 ) 1- and (MeBH 3 ) 1- can exhibit remarkably highly volatility, which creates unique hazards and handling challenges, especially when making measurements on solid samples under vacuum. Here we describe efforts to prepare new actinide borohydride complexes with attenuated volatility by adding bulkier benzyl (Bn) and cyclohexyl (Cy) substituents to boron. Reactions of ThCl 4 , UI 3 (thf) 4 , and NdI 3 with the mixed alkali metal salt Li/K(BnBH 3 )(thf) n yielded Th(BnBH 3 ) 4 (thf) 2 , U(BnBH 3 ) 4 (thf) 2 , and K[Nd(BnBH 3 ) 4 ], respectively. Notable amongst these, the reaction with UI 3 (thf) 4 proceeds via oxidation of U(III) to U(IV) despite the presence of reducing borohydride ligands. Similarly, reactions of the same metal halides with four equivalents of Li(CyBH 3 )(Et 2 O) n yielded Th(CyBH 3 ) 4 , U(CyBH 3 ) 4 (thf) 2 , and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ]. Single crystal X-ray diffraction studies of the M(BnBH 3 ) 4 (thf) 2 complexes with M = Th and U confirmed their formulations. Furthermore, the complexes have approximate D 2d point group symmetry and adopt bicapped hexagonal antiprismatic coordination geometries with axial thf ligands and κ 3 -BnBH 3 ligands bound in the equatorial plane. K[Nd(BnBH 3 ) 4 ] and [Li(Et 2 O) 3 ][Nd(CyBH 3 ) 4 ], which were prepared for comparison to U(III) complexes that were unsuccessfully targeted, were also structurally characterized to reveal complex anions with tetrahedral arrangements of trihydroborate ligands bound to Nd(III). Crystals obtained for Th(CyBH 3 ) 4 and U(CyBH 3 ) 4 (thf) 2 were not suitable for XRD studies, but 1 H and 11 B NMR spectra were consistent with their formulations. Collectively, these complexes represent rare examples of structurally characterized f-element trihydroborate complexes with carbon substituents other than methyl.
Here, this paper reviews various methods for studying surface tension and their applicability to fluoride and chloride molten salt systems, including a comparison of benefits and drawbacks. Such a comparison aids in experiment design based on desired factors such as scale, accuracy, and repeatability. A detailed review is presented for existing literature data regarding the surface tension of molten fluoride and chloride salts. These reference data were compiled and analyzed to determine cross-validated correlation equations for several alkali and alkaline earth fluoride and chloride salts as functions of temperature. These correlations are necessary for reliable multiphysics modeling approaches as well as accurate design and analysis of multiphase molten salt phenomena such as gas sparging and bubble formation/transport. This analysis supports the development of the thermophysical arm of the Molten Salt Thermal Properties Database (MSTDB-TP) managed by Oak Ridge National Laboratory.
In this study, waste forms were being explored for an electrochemical salt simulant, , referred to as ERV3, which is a high-LiCl/KCl salt containing simulated fission products (i.e., Sr, Cs, Nd) and Na to represent bond sodium from Experimental Breeder Reactor-II metallic fast reactor fuel. The goal was to find glassy systems that could be used to immobilize the salt in a single-step process. The envisionment of this process would be find a frit glass that could be added to the salt waste, heat treated, poured into waste canisters, and then stored for disposal. To perform this study, a literature review was conducted, the most promising seven systems were fabricated without the salt, and then mixed with salt simulant and heat treated under different processes. The criteria that were used to screen potential compositions included demonstrated alkali incorporation, could be melted at reasonably low temperature ( T ≤ 1000°C), and if the compositions had some demonstrated data for waste-form-related properties, that was a benefit. High marks were given for compositions that showed amorphous nature after slow cooling of samples containing ERV3.