Hugh C. De Long

Flammability, thermal stability, and phase change characteristics of several trialkylimidazolium salts

Room temperature ionic liquids (RTILs) have emerged as tunable and potentially “greener” solvents for a multitude of applications. To investigate the solvent properties and potential use as a thermal fluid, a study was initiated to determine the effects of anion type, C-2 hydrogen substitution, and alkyl chain length on the flammability, thermal stability, and phase change characteristics of 1,2,3-trialkylimidazolium room temperature ionic liquids. A Setaflash flashpoint apparatus was used to determine the flammabilities of the RTILs. No flashpoints were detected for any of the imidazolium based RTILs below 200 °C, the maximum temperature of the instrument. The thermal stabilities of the RTILs were measured using the technique of thermogravimetric analysis. The 1,2,3-trialkylimidazolium compounds exhibit slightly higher thermal stabilities than the comparable 1,3-dialkylimidazolium compounds; RTILs with nucleophilic anions decompose about 150 °C lower than RTILs with bulky fluoride containing anions; the alkyl chain length does not have a large effect on the thermal stability of the RTILs; and the pyrolysis decomposition exhibits higher thermal stabilities via a different mechanism than the oxidative decomposition. In addition, it was found that although the calculated onset temperatures were above 350 °C, significant decomposition does occur 100 °C or more below these temperatures. The phase change behaviors of several imidazolium based RTILs were characterized by differential scanning calorimetry. The melting points of the RTILs increased with increasing alkyl chain length. Most of the salts studied exhibited significant undercooling, which decreased as the length of the alkyl chain was increased. The hexafluorophosphate and bromide RTILs exhibited polymorphic and liquid crystalline behaviors as the alkyl chain length was increased above C10. The clearing point temperatures increased more rapidly with alkyl chain length than the melting point temperatures.

Regenerated silk fiber wet spinning from an ionic liquid solution

Regenerated silk fibroin from Bombyx mori silkworms was extruded into fibers from a 1-ethyl-3-methylimidazolium chloride ionic liquid solvent system; the drawn fibers rinsed in methanol exhibit alignment of the β-sheet crystallites along the fiber axis.

Improved Thermal Stability of Organically Modified Layered Silicates

Bromide-containing impurities were found to decrease the thermal stability of quaternary alkyl ammonium-modified layered silicates. Improved purification procedures completely removed bromide and led to a 20°C to >100°C increase in organic modified layered silicate thermal stability. Using mass spectrometry and thermal and electrochemical analysis, N,N-dimethyl-N,N-dioctadecyl quaternary ammonium-modified montmorillonite and fluorinated synthetic mica were found to degrade primarily through elimination and nucleophilic attack by these anions. The nature of residual bromides was identified and quantified, and the efficiency of removing these anions was found to be solvent dependent; sequential extraction, first ethanol then tetrahydrofuran, gave the best results. This exhaustive extraction method represents a viable alternative to the use of expensive, more thermally stable oniumion treatments for layered silicates.

Microelectrode Evaluation of Transition Metal‐Aluminum Alloy Electrodepositions in Chloroaluminate Ionic Liquids

Chronoamperometric data collected at a 250 μm tungsten microelectrode were analyzed under near-steady-state conditions to determine the composition of MAl x alloys (M = Co, Ni, Fe, Cu, and Ag) electrodeposited from 1.5:1.0 AlCl 3 :1-ethyl-3-methylimidazolium chloride room temperature ionic liquids. The analysis method relied on the fact that these alloys are produced by an underpotential deposition mechanism. Results were consistent with previous studies showing that the CoAl x , FeAl x , and CuAl x systems tended to produce alloys with x 1. Analysis of the NiAl x data was complicated by kinetic phenomena, while data analysis of the AgAl x system was precluded by dendritic growth of the electrodeposit. All the alloy systems showed complex anodic stripping voltammetric behavior, and the nature of the oxidation processes (e.g., metal anodization, alloy anodization, or selective dealloying) are different for electrodeposits produced in specific potential regimes. Nonlinear curve fitting of the chronoamperometric data to the appropriate short-time and long-time equations gave diffusion coefficients from 3.9 x 10 -7 to 8.3 x 10 -7 cm 2 s -1 for the transition metal ions in the ionic liquid electrolyte at ca. 22°C.

Dissolution of Biopolymers Using Ionic Liquids

Ionic liquids represent a unique class of solvents that offer unprecedented versatility and tunability. Nature has developed a wide variety of materials based upon both proteins and polysaccharides. Many of these materials have unique properties that are a function not only of the material identity but are also largely dictated by processing conditions. Recent work has shown the potential of ionic liquids as solvents for the dissolution and processing of biopolymers. In this research we have expanded upon the limited data available to date using several biopolymers including: silk, chitin, collagen and elastin.

Physical Properties of Substituted Imidazolium Based Ionic Liquids Gel Electrolytes

The physical properties of solid gel electrolytes of either polyvinylidene diflurohexafluoropropylene or a combination of polyvinylidene hexafluoropropylene and polyacrylic acid, and the molten salts 1-ethyl-3-methylimidazolium tetrafluoroborate, 1,2-dimethyl-3-n-propylimidazolium tetrafluoroborate, and the new molten salts 1,2-dimethyl-3-n-butylimidazolium tetrafluoroborate, and 1,2-dimethyl-3-n-butylimidazolium hexafluorophosphate were characterized by temperature dependent ionic conductivity measurements for both the pure molten salt and of the molten salt with 0.5 M Li+ present. Ionic conductivity data indicate that for each of the molten salts, the highest concentration of molten salt allowable in a single component polymer gel was 85%, while gels composed of 90%molten salt were possible when using both polyvinylidene hexafluorophosphate and polyacrylic acid. For polymer gel composites prepared using lithium containing ionic liquids, the optimum polymer gel composite consisted of 85% of the 0.5 M Li+/ionic liquid, 12.75% polyvinylidene hexafluoropropylene, and 2.25% poly (1-carboxyethylene). The highest ionic conductivity observed was for the gel containing 90%1-ethyl-3-methyl-imidazolium tetrafluoroborate, 9.08 mS/cm. For the lithium containing ionic liquid gels, their ionic conductivity ranged from 1.45 to 0.05 mS/cm, which is comparable to the value of 0.91 mS/cm, observed for polymer composite gels containing 0.5 M LiBF4 in propylene carbonate.

Process variables that control natural fiber welding: time, temperature, and amount of ionic liquid

A systematic study of variables that affect the fiber welding process is presented. Cotton cloth samples are treated with controlled amounts of 1-ethyl-3-methylimidazolium acetate for a series of times and temperatures. Diluting the ionic liquid with a volatile molecular co-solvent allows temporal and spatial control of the welding process not possible with neat ionic liquids. Materials are characterized by scanning electron microscopy, infrared spectroscopy, X-ray diffraction, and mechanical (tensile) testing. Results suggest careful management of process variables permits controlled, reproducible manipulation of chemical and physical properties.

3-(1-Methyl-3-imidazolio)propane­sulfonate: a precursor to a Brønsted acid ionic liquid

The title compound, C7H12N2O3S, is a zwitterion precursor to a Brønsted acid ionic liquid with potential as an acid catalyst. The C—N—C—C torsion angle of 100.05 (8)° allows the positively charged imidazolium head group and the negatively charged sulfonate group to interact with neighboring zwitterions, forming a C—H⋯O hydrogen-bonding network; the shortest among these interactions is 2.9512 (9) Å. The C—H⋯O interactions can be described by graph-set notation as two R 2 2(16) and one R 2 2(5) hydrogen-bonded rings.

Fluorescence monitoring of ionic liquid-facilitated biopolymer mobilization and reorganization.

Ionic liquid-facilitated mobilization and reorganization of biopolymers in natural fibrous materials is visualized by confocal fluorescent spectromicroscopy. Ionic liquid-based processes controllably fuse adjacent fibres while simultaneously leaving selected amounts of biopolymers in their native states. These processes generate congealed materials with extended intermolecular hydrogen bonding networks and enhanced properties.

Concurrent zero-dimensional and one-dimensional biomineralization of gold from a solution of Au3+ and bovine serum albumin

Abstract A technique was developed for preparing a novel material that consists of gold nanoparticles trapped within a fiber of unfolded proteins. These fibers are made in an aqueous solution that contains HAuCl4 and the protein, bovine serum albumin (BSA). By changing the ratio of gold to BSA in solution, two different types of outcomes are observed. At lower gold to BSA ratios (30–120), a purple solution results after heating the mixture at 80 °C for 4 h. At higher gold to BSA ratios (130–170), a clear solution containing purple fibers results after heating the mixture at 80 °C for 4 h. UV–Vis spectroscopy and light scattering techniques show growth in nanocolloid size as gold to BSA ratio rises above 100. Data indicate that, for the higher gold to BSA ratios, the gold is sequestered within the solid material. The material mass, visible by eye, appears to be an aggregation of smaller individual fibers. Scanning electron microscopy and transmission electron microscopy indicate that these fibers are primarily one-dimensional aggregates, which can display some branching, and can be as narrow as 400 nm in size. The likely mechanism for the synthesis of the novel material is discussed.