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At least 19 records

Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Preparing cellulose II nanocrystals (CNC II) requires a polymorph transformation of natural cellulose I feedstocks. The transformation is usually achieved via a process such as mercerization or dissolution–regeneration. This study demonstrated a new method to prepare CNC II directly from bleached kraft pulp (BKP, a commercially available cellulose I feedstock) in a mildly acidic lithium bromide trihydrate (MALBTH) system, a concentrated (~61 wt%) solution of LiBr in water with a very low concentration (2.5 mM) of sulfuric acid. First, the BKP was treated in the MALBTH system to generate a cellulose II hydrolysis solid residue (CHR) with a yield of 64–86%, during which the selective hydrolysis of disordered cellulose and the polymorph transformation were completed simultaneously. Then, subsequent oxidation of the CHR by ammonium persulfate (APS, 0.1–0.6 M) resulted in the CNC II with high yield (up to 62%), high crystallinity (over 90%), rich surface carboxyl group (0.3–1.2 mmol g-1 cellulose), excellent colloidal stability (up to -59 mV zeta potential), and high thermal stability. The CNC II had a tunable length (26–57 nm), determined by the conditions of the MALBTH hydrolysis and the APS oxidation, but similar lateral dimension (8–10 nm). The characterization of the CHR by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy verified the polymorphic transformation from cellulose I to II during the MALBTH treatment. The swelling of the BKP in the MALBTH enabled cellulose crystallites to slide and reassemble, which completed the rearrangement of cellulose chains from parallel to anti-parallel conformation (polymorph transformation from cellulose I to II). This study provided an efficient and green method to produce cellulose II nanocrystals with controllable aspect ratios via the simultaneous hydrolysis and polymorph transformation of cellulose I feedstocks.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Anionic Effects on Concentrated Aqueous Lithium Ion Dynamics

In this article, the structural dynamics, chemical reactivity, anisotropy, diffusivity, viscosity, and density were measured for concentrated lithium salt solutions, including lithium chloride (LiCl), lithium bromide (LiBr), lithium nitrite (LiNO 2 ), and lithium nitrate (LiNO 3 ), with methyl thiocyanate as an infrared vibrational probe molecule, using two-dimensional infrared spectroscopy (2D IR), nuclear magnetic resonance (NMR) spectroscopy, and viscometry. 2D IR, NMR, and viscosity results show that LiNO 2 exhibits longer correlation times, lower diffusivity, and nearly four times greater viscosity when compared to the other lithium salt solutions of the same concentration, suggesting that nitrite anions may strongly facilitate structure formation via strengthening water-ion interactions, directly impacting bulk solution properties at sufficiently high concentrations. Additionally, the LiNO 2 and LiNO 3 solutions show significantly reduced chemical reactivity with respect to lithium cations coordinating with the methyl thiocyanate when compared to the lithium halide salts.

2D IR↗

Design, evaluation and recommedation effort relating to the modification of a residential 3-ton absorption cycle cooling unit for operation with solar energy

The possible use of solar energy powered absorption units to provide cooling and heating of residential buildings is studied. Both, the ammonia-water and the water-lithium bromide cycles, are considered. It is shown that the air cooled ammonia water unit does not meet the criteria for COP and pump power on the cooling cycle and the heat obtained from it acting as a heat pump is at too low a temperature. If the ammonia machine is water cooled it will meet the design criteria for cooling but can not supply the heating needs. The water cooled lithium bromide unit meets the specified performance for cooling with appreciably lower generator temperatures and without a mechanical solution pump. It is recommeded that in the demonstration project a direct expansion lithium bromide unit be used for cooling and an auxiliary duct coil using the solar heated water be employed for heating.

Merrick, R. H.↗

Absorption heat pump for space applications

In the first part, the performance of the Absorption Heat Pump (AHP) with water-sulfuric acid and water-magnesium chloride as two new refrigerant-absorbent fluid pairs was investigated. A model was proposed for the analysis of the new working pairs in a heat pump system, subject to different temperature lifts. Computer codes were developed to calculate the Coefficient of Performance (COP) of the system with the thermodynamic properties of the working fluids obtained from the literature. The study shows the potential of water-sulfuric acid as a satisfactory replacement for water-lithium bromide in the targeted temperature range. The performance of the AHP using water-magnesium chloride as refrigerant-absorbent pair does not compare well with those obtained using water-lithium bromide. The second part concentrated on the design and testing of a simple ElectroHydrodynamic (EHD) Pump. A theoretical design model based on continuum electromechanics was analyzed to predict the performance characteristics of the EHD pump to circulate the fluid in the absorption heat pump. A numerical method of solving the governing equations was established to predict the velocity profile, pressure - flow rate relationship and efficiency of the pump. The predicted operational characteristics of the EHD pump is comparable to that of turbomachinery hardware; however, the overall efficiency of the electromagnetic pump is much lower. An experimental investigation to verify the numerical results was conducted. The pressure - flow rate performance characteristics and overall efficiency of the pump obtained experimentally agree well with the theoretical model.

Nguyen, Tuan↗

Development of a solar powered residential air conditioner (General optimization)

A commercially available 3-ton residential Lithium Bromide (LiBr) absorption air conditioner was modified for use with lower temperature solar heated water. The modification included removal of components such as the generator, concentration control chamber, liquid trap, and separator; and the addition of a Chrysler designed generator, an off-the-shelf LiBr-solution pump. The design goal of the modified unit was to operate with water as the heat-transfer fluid at a target temperature of 85 C (185 F), 29.4 C (85 F) cooling water inlet, producing 10.5 kW (3 tons) of cooling. Tests were performed on the system before and after modification to provide comparative data. At elevated temperatures (96 C, 205 F), the test results show that Lithium Bromide was carried into the condenser due to the extremely violent boiling and degraded the evaporator performance.

Lowen, D. J.↗

Simulation model of a single-stage lithium bromide-water absorption cooling unit

A computer model of a LiBr-H2O single-stage absorption machine was developed. The model, utilizing a given set of design data such as water-flow rates and inlet or outlet temperatures of these flow rates but without knowing the interior characteristics of the machine (heat transfer rates and surface areas), can be used to predict or simulate off-design performance. Results from 130 off-design cases for a given commercial machine agree with the published data within 2 percent.

Miao, D.↗

Halogenation of used aluminum matrix test reactor fuel – a bench-scale demonstration with surrogate materials

In this work, experiments with surrogate materials were performed at bench scale to demonstrate a halogenation technique applicable to treatment of used aluminum matrix test reactor fuel. The technique involves dissolution and separation of aluminum from used aluminum matrix test reactor fuel in molten-halide salt systems prior to treatment and disposition of the fuel’s uranium and fission products. Demonstration of the halogenation technique was performed with neodymium metal as a non-radiological surrogate for uranium metal. Experiments involved blending forms of aluminum and neodymium metal with ammonium and lithium chloride or ammonium and lithium bromide, which upon heating decomposed into ammonia gas and the respective hydrogen chloride or bromide gas. The latter reacted with the metals to form the respective aluminum and neodymium halides. At elevated temperatures, aluminum halides gasified away from the respective neodymium halides, which fused with their respective lithium halides. Samples of fused and distillate salts were collected and analyzed, yielding extents of aluminum removal that ranged from 94.5–98.2% for chlorination runs and 91.4–97.8% for bromination runs. No neodymium was detected in the distillate fractions. Some experiments were repeated with excess reactants, and a portion of aluminum chloride distillate was processed into a consolidated waste form.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

EGS Collab Testbed 1: Second Set Tracer Test Results

The EGS Collab project is developing ~10-20 m-scale field sites where fracture stimulation and flow models can be validated against controlled, small-scale, in-situ experiments. The first multi-well experimental site was established at the 4850 level in the Homestake Mine in Lead, South Dakota, where hydraulic fractures were created at an injection well drilled sub-horizontal from the drift. This file contains the second set of tracer data (also include the data uploaded previously, https://gdr.openei.org/submissions/1128) for the EGS Collab testbed. The tracer tests were conducted during October 2018 - November 2019. Injected tracers include DNA, C-dots (fluorescein nano particles), fluorescein, rhodamine-b, sodium chloride, lithium bromide and cesium iodine. The tracers have been detected in three flowing wells located about 7.5 to 9 meters away from the injection interval. The tracer breakthrough curves from these locations have been adjusted to account for the residence time in the injection and production tubing. The details about the tracer test can be found in Background and Methods of Tracer Tests (Mattson et al. (2019,a,b)) (also included in this package). References Mattson, E.D., Neupane, G., Plummer, M.A., Hawkins, A., Zhang, Y. and the EGS Collab Team 2019a. Preliminary Collab fracture characterization results from flow and tracer testing efforts. In Proceedings 44th Workshop on Geothermal Reservoir Engineering, edited, Stanford University, Stanford, California. Mattson, E.D., Neupane, G., Hawkins, A., Burghardt, J., Ingraham, M., Plummer, M., and the EGS Collab Team, 2019b. Fracture tracer injection response to pressure perturbations at an injection well. GRC Transactions, Vol. 43, 2019. Neupane, Ghanashyam, Earl Mattson, Adam Hawkins, Mitchell Plummer, and Yuran Zhang. EGS Collab Testbed 1: Tracer data sets. No. 1128. DOE Geothermal Data Repository; Idaho National Laboratory, 2019.

15 GEOTHERMAL ENERGY↗

Hydrogen-Bromine Secondary Battery

A secondary battery is described utilizing hydrogen and halogen as primary reactants. It comprises inert anode and cathode initially contacting an aqueous solution of an acid and an alkali metal bromide. The hydrogen generated during charging of the cell is stored as gas, while the bromine becomes dissolved predominantly in the lower layers of the acid electrolyte. Preferred components are phosphoric acid and lithium bromide.

England, C.↗

Anion and Cation Size Effects on Viscoelasticity and Ion Transport of Imine Vitrimer Electrolytes

Vitrimers are a subclass of covalent adaptable networks where bond exchange occurs without breaking, thereby offering polymer materials with enhanced mechanical strength, thermal stability, and reprocessability compared to conventional electrolytes. Despite recent progress, we lack a complete understanding of the role of ions in controlling the physical and chemical properties of vitrimers. In this work, we study how different salts affect the viscoelasticity, morphology, and ionic conductivity of imine vitrimers. Our results show that addition of salt decreases relaxation times at elevated temperatures due to the catalytic effect of the cations, with smaller cations leading to faster relaxation. However, the activation energy for terminal relaxation increases with smaller cation size. This apparent discrepancy is attributed to the complex interplay among bond exchange kinetics, chain diffusion, and salt dissociation. Anions act as plasticizers by reducing the shear modulus, except lithium bromide. Ionic conductivity increases with larger anions due to smaller salt dissociation energies, whereas the cation type has a minor impact as polymer segmental dynamics dominate ionic transport. Imine-based vitrimers are reprocessable and recyclable, maintaining original mechanical properties and ionic conductivity after recovery. Mixed salt vitrimers exhibited tunable viscoelasticity and ionic conductivity intermediate to the analogous pure salt systems. Altogether, this work highlights the role of salt in the dynamic and conductive properties of imine vitrimers.

Anions↗

Exfoliation of Cu-Containing Poly(triazine imide): From Three-Dimensional to Two-Dimensional Particle Morphology

Controlling the morphological parameters of extended covalent organic frameworks remains challenging and represents an important yet often elusive metric of consideration. Typically, carbon nitride materials possess local ordering but remain largely amorphous in terms of their long-range order and orientation. This study probes the synthesis of a crystalline carbon nitride, poly(triazine imide) lithium bromide which possesses an atomically-precise extended structure, and demonstrates its exfoliation into a two-dimensional hexagonal sheet-like morphology. Furthermore, a previously unreported carbon nitride material, poly(triazine imide) copper bromide, or PTI-CuBr, was developed through an additional flux-assisted cation-exchange process and is shown to retain its internal Cu cations during solvothermal exfoliation. Characterization by dynamic light scattering and high-angle annular dark-field scanning electron microscopy reveals the morphological changes and captures the high aspect ratio of the thin carbon nitride sheets with <10 nm thickness while maintaining hundreds of nm in width. Additional characterization by energy-dispersive spectroscopy and X-ray photoelectron spectroscopy confirms that the Cu:Br:N molar ratio was maintained within the extended layers throughout the exfoliation process. This top-down synthesis approach differs from typical methods that isolate thin sheets for subsequent metal−cation coordination and illustrates the importance of maintaining oxygen-free conditions to minimize copper clustering. Thus, this new approach is demonstrated to provide a consistent and more homogeneous occupancy of the PTI pore spaces throughout the carbon nitride framework.

Exfoliation↗

Equilibrium Thermodynamic Properties of Aqueous Solutions of Ionic Liquid 1-Ethyl-3-Methylimidazolium Methanesulfonate [EMIM][MeSO3]

Abstract The ionic liquid 1-ethyl-3-methylimidazolium methanesulfonate ([EMIM][MeSO 3 ]) has been considered as a promising alternative desiccant to triethylene glycol and lithium bromide commonly used in the industry. In this paper, the water activity coefficient of this binary system was measured from 303 K to 363 K with water concentration from 18% to 92%. The interaction energies between the ionic liquid molecules ( $${g}_{22}$$ g 22 ) and between the ionic liquid and water molecules ( $${g}_{12}$$ g 12 ) for the [EMIM][MeSO 3 ]/water binary system were determined from the water activity coefficient data using the Non-Random Two-Liquid (NRTL) model. The magnitude of the interaction energy between the [EMIM][MeSO 3 ] and water molecules ( $${g}_{12}$$ g 12 ) was found to be in the range of 45~49 kJ/mol, which was about 20% larger than that between the water molecules ( $${g}_{11}$$ g 11 ) in the [EMIM][MeSO 3 ]/water system. The large ( $${g}_{12}$$ g 12 ) can explain many observed macroscopic thermodynamic properties such as strong hygroscopicity in the ionic liquid [EMIM][MeSO 3 ]. These interaction energies were used to determine the heat of desorption of the [EMIM][MeSO 3 ]/water system, and the obtained heat of desorption was in good agreement with that calculated from the conventional Clausius-Clapeyron Equation.

42 ENGINEERING↗

Measured performance of a 3 ton LiBr absorption water chiller and its effect on cooling system operation

A three ton lithium bromide absorption water chiller was tested for a number of conditions involving hot water input, chilled water, and the cooling water. The primary influences on chiller capacity were the hot water inlet temperature and the cooling water inlet temperature. One combination of these two parameters extended the output to as much as 125% of design capacity, but no combination could lower the capacity to below 60% of design. A cooling system was conceptually designed so that it could provide several modes of operation. Such flexibility is needed for any solar cooling system to be able to accommodate the varying solar energy collection and the varying building demand. It was concluded that a three-ton absorption water chiller with the kind of performance that was measured can be incorporated into a cooling system such as that proposed, to provide efficient cooling over the specified ranges of operating conditions.

Namkoong, D.↗

Optimization of absorption air-conditioning for solar energy applications

Improved performance of solar cooling systems using the lithium bromide water absorption cycle is investigated. Included are computer simulations of a solar-cooled house, analyses and measurements of heat transfer rates in absorption system components, and design and fabrication of various system components. A survey of solar collector convection suppression methods is presented.

Perry, E. H.↗