Time-resolved energy transfer from single chloride-terminated nanocrystals to graphene
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36 MATERIALS SCIENCE↗
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Results for “CHLORIDES”
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Uranium Adsorbent Fibers Prepared by Atom-Transfer Radical Polymerization (ATRP) from Poly(vinyl chloride)- co -chlorinated Poly(vinyl chloride) (PVC- co -CPVC) Fiber
The need to secure future supplies of energy attracts researchers in several countries to a vast resource of nuclear energy fuel: uranium in seawater (estimated at 4.5 billion tons in seawater). In this study, we developed effective adsorbent fibers for the recovery of uranium from seawater via atom-transfer radical polymerization (ATRP) from a poly- (vinyl chloride)-co-chlorinated poly(vinyl chloride) (PVC-co-CPVC) fiber. ATRP was employed in the surface graft polymerization of acrylonitrile (AN) and tert-butyl acrylate (tBA), precursors for uranium-interacting functional groups, from PVC-co-CPVC fiber. The [tBA]/[AN] was systematically varied to identify the optimal ratio between hydrophilic groups (from tBA) and uranyl-binding ligands (from AN). The best performing adsorbent fiber, the one with the optimal [tBA]/[AN] ratio and a high degree of grafting (1390%), demonstrated uranium adsorption capacities that are significantly greater than those of the Japan Atomic Energy Agency (JAEA) reference fiber in natural seawater tests (2.42-3.24 g/kg in 42 days of seawater exposure and 5.22 g/kg in 49 days of seawater exposure, versus 1.66 g/kg in 42 days of seawater exposure and 1.71 g/kg in 49 days of seawater exposure for JAEA). Adsorption of other metal ions from seawater and their corresponding kinetics were also studied. The grafting of alternative monomers for the recovery of uranium from seawater is now under development by this versatile technique of ATRP.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
XAFS Studies of Ni Ta and Nb Chlorides in the Ionic Liquid 1-Ethyl-3-Methyl Imidazolium Chloride / Aluminum Chloride
The structures of anhydrous nickel, niobium, and tantalum chlorides have been investigated in situ in acidic and basic ionic liquids (ILs) of 1-methyl-3-ethylimidazolium chloride (EMIC)/AlCl{sub 3} with X-ray absorption spectroscopy (XAS). The coordination of NiCl{sub 2} changes from tetrahedral in basic solution to octahedral in acidic solution. The NiCl{sub 2} is a strong Lewis acid in that it can induce the AlCl{sub 3} to share its chlorides in the highly acidic IL, forming a structure with six near Cl{sup -} ions and eight further distant Al ions which share the chloride ions surrounding the Ni{sup 2+}. When Nb{sub 2}Cl{sub 10}, a dimer, is added to the acidic or basic solution, the dimer breaks apart and forms two species. In the acid solution, two trigonal bipyramids are formed with five equal chloride distances, while in the basic solution, a square pyramid with four chlorides forming a square base and one shorter axial chloride bond. Ta{sub 2}Cl{sub 10} is also a dimer and divides into half in the acidic solution and forms two trigonal bipyramids. In the basic solution, the dimer breaks apart but the species formed is sufficiently acidic that it attracts two additional chloride ions and forms a seven coordinated tantalum species.
36 MATERIALS SCIENCE↗
An XAFS Study of Tantalum Chloride in the Ionic Liquid 1-ethyl-3-methyl Imidazolium Chloride/ aluminum Chloride
Tantalum chloride was studied with extended X-ray absorption fine structure spectroscopy (XAFS) in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride ionic liquids (ILs). Anhydrous Ta2Cl10 is more soluble in the basic solution than in the acidic solution and the X-ray absorption data shows that the coordination shell of chlorides around the tantalum is larger in the basic solution. In the acidic solution, tantalum has five chlorides in its coordination shell while in the basic solution; the tantalum is coordinated by seven chlorides. This indicates that the Lewis acidity of the tantalum chloride causes the Ta to coordinate differently in the acidic and the basic solutions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
An XAFS study of nickel chloride in the ionic liquid 1-ethyl-3-methyl imidazolium chloride/ aluminum chloride
Nickel chloride was studied with cyclic voltammetry and X-ray absorption spectroscopy in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride (EMIC) ionic liquids. Acidic melts display metal stripping peaks which are not observed in the basic melt. EXAFS analysis shows that the nickel is tetrahedrally coordinated with chloride ions in the basic solution. In the acidic solution the nickel is coordinated by six chloride ions that are also associated with aluminum ions.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Selective Monooxidation of Light Alkanes Using Chloride and Iodate
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catalysis (homogeneous), catalysis (heterogeneous)↗
An XAFS Study of Niobium chloride in the ionic liquid 1-ethyl-3-methyl imidazolium chloride/ aluminum chloride
Niobium chloride was studied with extended X-ray absorption fine structure spectroscopy (EXAFS) in acidic and basic aluminum chloride/1-ethyl-3-methyl imidazolium chloride (EMIC) ionic liquids. Although anhydrous Nb2Cl10 is more soluble in the basic melt than in the acidic melt, the EXAFS data shows that the coordination shell around the niobium does not change in the different ionic liquids. Both the acidic and basic melts show a coordination of five chlorides in the first shell. This indicates that in this series of ionic liquids, the Nb2Cl10 breaks up into two NbCl5 entities in both the acidic and the basic melts.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Anolyte studies of the magnesium electrode in molten mixtures of lithium chloride, potassium chloride, and magnesium chloride
Anolyte studies of magnesium electrode in molten mixtures of lithium chloride, potassium chloride, and magnesium chloride
Thaller, L. H.↗
Characterisation and heat treatment of chloride-contaminated and humidified PuO2 samples
To mimic the reactions that have occurred between plutonium dioxide (PuO2) and degraded polyvinyl chloride during prolonged storage, batches of PuO2 powders with varying specific surface area (4-38m2 g1) were exposed to dry hydrogen chloride gas forming a surface-sorbed exchangeable chloride species that was readily leached by dilute caustic solution. One batch was also humidified under a 95% relative humidity atmosphere. Heat treatment at temperatures between 100 and 950 C steadily reduced the leachable chloride content at least when the initial leachable chloride surface coverage was calculated to be > 0.5 monolayer (ML). Variations between samples are attributed to differences in surface area as well as production route and period of interim storage in air or humidified atmospheres. The data are consistent with surface species and reactions proposed in the literature for HCl adsorption on to TiO2. This indicates that it is interactions between hydrogen chloride/chloride and water/hydroxyl species on the PuO2 surface that are key to understanding the behaviour of these materials when heated in a furnace. These data will inform the design of a future thermal stabilisation process for chloride-contaminated PuO2.
Sutherland-Harper, Sophie↗
Mechanism and Kinetics of Stibnite Chloridizing with Calcium Chloride-Oxygen at 500 °C to 650 °C
Copper concentrates with high levels of toxic impurity elements such as As, Sb Bi, must be pretreated before processing in the current smelting/converting refineries. The classical method for the pretreatment of dirty copper concentrates is partial oxidizing roasting, where the impurities are eliminated through the gas phase. However, volatilization of antimony and bismuth in conventional roasting processes using air or oxygen-deficient air is hardly achieved since antimony and bismuth remain in the calcine as non-volatile oxides. The chloridizing of stibnite with calcium chloride was studied as an alternative to volatilize antimony from impure copper concentrates because the vapor pressure of antimony chloride is higher than the vapor pressures of antimony oxide or sulfide at low temperatures. Thus, in the present work, the kinetic study of chloridizing of antimony from stibnite using calcium chloride as the chloridizing agent was studied at roasting temperatures 500 °C to 650 °C. The salient aspects determined in this study are that the chloridizing of stibnite starts with the formation of Sb{sub 2}O{sub 3} followed by the chloridizing of this oxide by chlorine gas. The formation of antimony oxide Sb{sub 6}O{sub 13} deters the complete elimination of antimony from stibnite. By using the unreacted shrinking core model 1 − (1 − α){sup 1/3} = k{sub r}t, the chloridizing rate of stibnite with CaCl{sub 2} and oxygen was found to be of 0.6 order with respect to the oxygen partial pressure, and the calculated energy of activation is 62 kJ mol{sup −1} in the range from 500 °C to 650 °C.
36 MATERIALS SCIENCE↗
The Structure of Nickel Chloride in the Ionic Liquid 1-Ethyl-3-methyl Imidazolium Chloride/Aluminum Chloride: X-ray Absorption Spectroscopy
The structure of anhydrous nickel chloride in the ionic liquid 1-ethyl-3-methyl imidazolium chloride and aluminum chloride has been investigated with extended X-ray absorption fine structure (EXAFS) in both Lewis acid and Lewis base solutions. The EXAFS data of NiCl{sub 2} {center_dot} 6H{sub 2}O crystals were also recorded and analyzed to demonstrate the difference file technique. The difference file technique is used to obtain the structural information for the very closely spaced coordination shells of chloride and oxygen in NiCl{sub 2} {center_dot} 6H{sub 2}O and they are found to agree very closely with the X-ray diffraction data. The difference file technique is then used to analyze the nickel chloride in the ionic liquid solutions. Even though anhydrous NiCl{sub 2} is more soluble in the basic solution than in the acidic solution, the EXAFS data show a single coordination of four chlorides in a tetrahedron around the nickel atom in the basic solution. In a weak acid solution, there are six chlorides in a single octahedral coordination shell around the nickel. However, in a strong acid solution, in addition to the octahedral chloride-coordination shell, there is a second coordination shell of eight aluminum atoms in the form of a simple cube.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Determination of activity coefficient of lanthanum chloride in molten LiCl-KCl eutectic salt as a function of cesium chloride and lanthanum chloride concentrations using electromotive force measurements
Not Available
Bagri, Prashant (ORCID:0000000333610000)↗
Exploring the cell: Sodium (beta-alumina) cupric chloride - Aluminum chloride - Sodium chloride between 136 and 200 C
Experiments were done with a molten-salt catholyte (initially CuCl2 in AlCl3-NaCl) separated from molten Na by beta alumina. The open-circuit reduction potentials were 4.3 and 3 volts for Cu++ and Cu+, respectively. High polarization and nonrechargeability characterized the cell's operation. The cell's ohmic resistance during discharge was higher than what would be expected from only the ionic resistance of the beta-alumina.
Miller, R. O.↗
Re‐establishing the paradigm for evaluating halide salt compatibility to study commercial chloride salts at 600°C–800°C
Abstract Chloride salts are one candidate for a >700°C concentrating solar power (CSP) cycle, however, many reports from the literature suggest very high reaction rates between chloride salts and structural alloys. Historically, a specific methodology was established for evaluating halide salt compatibility based on solution kinetics. This study returned to that paradigm where the salts are purified and evaluated in sealed capsules before moving to a flowing experiment to determine a true corrosion rate in a temperature gradient for a commercial K–Mg–Na chloride salt. Isothermal testing focused on Ni‐based alloys 230 and 600 at 600°C–800°C. The results indicated there were promising combinations of salt chemistry, temperature, and alloy composition that reduce the extent of reaction. The results of the first monometallic thermal convection loop of alloy 600 run for 1,000 hr with a peak temperature of 700°C showed low attack with rates ≤9 µm/yr.
Pint, Bruce A.↗
Chloride diffusivity, chloride threshold, and corrosion initiation in reinforced alkali-activated mortars: Role of calcium, alkali, and silicate content
The aim of this study is to investigate systematically the chloride diffusivity and chloride threshold of a wide range of calcium-rich and fly ash-dominated alkali-activated samples in light of their compositional differences. To this end, the effects of various fly ash (FA)-to-slag ratios, of alkali concentrations and of silicate content in the activator were investigated. The electrochemical aspects of the passive samples were also assessed. Results show the prominent role of calcium in the matrix to reduce the chloride diffusivity. While higher alkali concentration increased the porosity and chloride diffusivities in general, lower modulus ratios provided considerably better performance in the FA-dominated samples. Chloride threshold values range between 0.19 (wt% binder mass) for calcium-rich mortars fabricated at low levels of alkalinities and 0.69 for FA-dominated mortars fabricated with highly alkaline activators. Half-cell potential and polarization resistance of alkali-activated samples were in general lower than their Portland cement counterparts.
36 MATERIALS SCIENCE↗