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Richard B Kaner

Publications and source records attributed to Richard B Kaner.

17 recordsLinked to original sources

Direct electrical measurement of the conversion of metal acetates to metal sulfides by hydrogen sulfide.

Copper acetate and related metal salt films react directly with hydrogen sulfide at room temperature to form metal sulfides, resulting in conductivity changes as large as 108. The observed changes in conductivity are related to the solubility product constant (Ksp) and the difference in conductivity between the metal salt and the resulting metal sulfide. A smaller Ksp indicates a more stable metal sulfide and, therefore, greater metal salt reactivity. Polyaniline nanofiber/metal salt composites were also examined and show metal sulfide conversion with changes in resistance up to 106. The direct electrical measurement of the conversion of metal salt to metal sulfide has the potential to be the basis of a new type of sensitive, thin-film chemical sensor.

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Hydrogen sensors based on conductivity changes in polyaniline nanofibers.

Hydrogen causes a reversible decrease in the resistance of a thin film of camphorsulfonic acid doped polyaniline nanofibers. For a 1% mixture of hydrogen in nitrogen, a 3% decrease in resistance is observed (DeltaR/R = -3%). The hydrogen response is completely suppressed in the presence of humidity. In contrast, oxygen does not inhibit the hydrogen response. A deuterium isotope effect on the sensor response is observed in which hydrogen gives a larger response than deuterium: (DeltaR/R)H/(DeltaR/R)D = 4.1 +/- 0.4. Mass sensors using nanofiber films on a quartz crystal microbalance also showed a comparable deuterium isotope effect: DeltamH/DeltamD = 2.3 +/- 0.2 or DeltanH/DeltanD = 4.6 +/- 0.4 on a molar basis. The resistance change of polyaniline nanofibers is about an order of magnitude greater than conventional polyaniline, consistent with a porous, high-surface-area nanofibrillar film structure that allows for better gas diffusion into the film. A plausible mechanism involves hydrogen bonding to the amine nitrogens along the polyaniline backbone and subsequent dissociation. The inhibitory effect of humidity is consistent with a stronger interaction of water with the polyaniline active sites that bind to hydrogen. These data clearly demonstrate a significant interaction of hydrogen with doped polyaniline and may be relevant to recent claims of hydrogen storage by polyaniline.

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Enhanced solid-state metathesis routes to carbon nanotubes.

Ignition of three solids creates multiwalled carbon nanotubes in seconds. A solid-state metathesis (exchange) reaction between hexachloroethane (C2Cl6) and lithium acetylide (Li2C2) with 5% cobalt dichloride (CoCl2) added as an initiator produces up to 7% carbon nanotubes, as observed via transmission electron microscopy. Using the concept that sulfur can promote nanotube growth, the reaction yield can be increased to 15% by switching to CoS as the initiator. The more readily available, inexpensive calcium carbide (CaC2) can be substituted for lithium acetylide while maintaining comparable yields. Switching initiators to FeS can be used to further enhance the yield. A systematic study of the C2Cl6/CaC2 reaction system indicates that a yield up to 25% can be realized by using 6% FeS as the initiator. Reaction temperatures for the C(2)Cl6/CaC2 system of up to 3550 degrees C are calculated using thermodynamic data assuming quantitative yield and adiabatic conditions.

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Shape and aggregation control of nanoparticles: not shaken, not stirred.

The aggregation of nanoparticles during synthesis, particularly the effect of mechanical agitation, is investigated from a viewpoint of nucleation using a conjugated polymer, polyaniline, as an example. Homogeneous nucleation of polyaniline results in nanofibers, while heterogeneous nucleation leads to granular particulates. Mechanical agitation, which is a common method for disrupting aggregates, instead dramatically triggers aggregation during the synthetic process and favors the formation of granular particulates. Correlating the shape and aggregation of polyaniline nanoparticles with the mode of nucleation, a new aggregation mechanism is proposed in which aggregation is triggered by heterogeneous nucleation. The mechanism may be quite general as indicated by experiments with other materials such as silica nanoparticles. Highly dispersible polyaniline nanofibers can now be reproducibly prepared from a conventional reaction simply by not mechanically agitating the reaction and carrying it out at an elevated temperature. This work may prove to be of great value in reproducibly synthesizing nanoparticles with well-controlled sizes and shapes and in effectively preventing aggregation in chemical, pharmaceutical, and materials production processes.

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The intrinsic nanofibrillar morphology of polyaniline.

Polyaniline nanofibers are shown to form spontaneously during the chemical oxidative polymerization of aniline. The nanofibrillar morphology does not require any template or surfactant, and appears to be intrinsic to polyaniline synthesized in water. Two approaches--interfacial polymerization and rapidly-mixed reactions--have been developed to prepare pure nanofibers. The key is suppressing the secondary growth that leads to agglomerated particles. The effects of different dopant acids and solvents are discussed. Changing the dopant acid can be used to tune the diameters of the nanofibers between about 30 and 120 nm. Changing the organic solvent in interfacial polymerization reactions has little effect on the product. A brief discussion of the processibility of the nanofibers is presented. The possibility of creating nanofibrillar structures for selected polyaniline derivatives is also demonstrated.

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Osmium diboride, an ultra-incompressible, hard material.

The need for wear- and scratch-resistant materials drives the quest for new superhard materials. In this work, we apply two design parameters to identify ultra-incompressible, superhard materials-high valence electron density and high bond covalency. Our first example of such a material is OsB2. The bulk modulus of OsB2 was measured using in situ high-pressure X-ray diffraction and was determined to be in the range of 365-395 GPa. While this value is slightly less than that of the bulk modulus of diamond, due to the anisotropic crystal structure of OsB2, the axis compressibility in the orthorhombic c-direction is less than the axis compressibility found in diamond. OsB2 also scratches the surface of a sapphire window, indicating that the hardness of OsB2 exceeds 2000 kg/mm2.

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Processable stabilizer-free polyaniline nanofiber aqueous colloids.

Aqueous polyaniline colloids can be readily prepared by purifying polyaniline nanofibers and controlling the pH and self-stabilized via electrostatic repulsions without the need for any chemical modification or steric stabilizer, thus providing a simple and environmentally friendly way to process the conducting polymer in its conductive state both in bulk and at the nanometre level.

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Polyaniline nanofiber/gold nanoparticle nonvolatile memory.

A nonvolatile plastic digital memory device based on nanofibers of the conjugated polymer polyaniline decorated with gold nanoparticles is reported. The device has a simple structure consisting of the plastic composite film sandwiched between two electrodes. An external bias is used to program the ON and OFF states of the device that are separated by a 3-orders-of-magnitude difference in conductivity. ON-OFF switching times of less than 25 ns are observed by electrical pulse measurements. The devices possess prolonged retention times of several days after they have been programmed. Write-read-erase cycles are also demonstrated. The switching mechanism is attributed to an electric-field-induced charge transfer from the polyaniline nanofibers to the gold nanoparticles. The active polymer layer is created by growing nanometer size gold particles within 30-nm-diameter polyaniline nanofibers using a redox reaction with chloroauric acid. This device combines two exciting research areas--nanoparticles and conducting polymers--to form a novel materials system with unique functionality.

Aniline Compounds↗

Flash welding of conducting polymer nanofibres.

The absorption of light by a material generates heat through non-radiative energy dissipation and exothermic photochemical reactions. In nanostructured materials, the heat generated through photothermal processes will be confined within the individual nanostructures when heat transfer to neighbouring nanostructures and the environment is slow. This leads to unprecedented photothermal effects that cannot be observed in bulk materials, especially when a strong, pulsed light source is used. Here we demonstrate an enhanced photothermal phenomenon with conducting polymer nanofibres in which a camera flash causes instantaneous welding. Under flash irradiation, polyaniline nanofibres 'melt' to form a smooth and continuous film from an originally random network of nanofibres. This photothermal effect can be used to form asymmetric nanofibre films, to melt-blend polymer-polymer nanocomposites rapidly and to photo-pattern polymer nanofibre films.

Microscopy, Electron↗

Nanostructured polyaniline sensors.

The conjugated polymer polyaniline is a promising material for sensors, since its conductivity is highly sensitive to chemical vapors. Nanofibers of polyaniline are found to have superior performance relative to conventional materials due to their much greater exposed surface area. A template-free chemical synthesis is described that produces uniform polyaniline nanofibers with diameters below 100 nm. The interfacial polymerization can be readily scaled to make gram quantities. Resistive-type sensors made from undoped or doped polyaniline nanofibers outperform conventional polyaniline on exposure to acid or base vapors, respectively. The nanofibers show essentially no thickness dependence to their sensitivity.

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A general chemical route to polyaniline nanofibers.

Uniform polyaniline nanofibers readily form using interfacial polymerization without the need for templates or functional dopants. The average diameter of the nanofibers can be tuned from 30 nm using hydrochloric acid to 120 nm using perchloric acid as observed via both scanning and transmission electron microscopy. When camphorsulfonic acid is employed, 50 nm average diameter fibers form. The measured Brunauer-Emmett-Teller surface area of the nanofibers increases as the average diameter decreases. Further characterization including molecular weight, optical spectroscopy, and electrical conductivity are presented. Interfacial polymerization is shown to be readily scalable to produce bulk quantities of nanofibers.

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Rapid solid-state metathesis routes to aluminum nitride.

Metathesis (exchange) reactions offer the possibility of controlling temperature through a judicious choice of precursors. Here, a reaction between AlCl(3) and Ca(3)N(2) is found to produce phase-pure aluminum nitride (AlN) in seconds. The CaCl(2) byproduct salt, whose formation drives this highly exothermic reaction, is simply washed away after reaction completion. SEM images demonstrate that the AlN product is a micron-sized powder, while TEM shows well-formed crystallites. Thermodynamic calculations indicate that a reaction temperature of 2208 K could be reached under adiabatic conditions. Using an in situ thermocouple and a stainless steel reactor vessel to hold the precursors, a reaction temperature of 1673 K is measured 0.8 s after initiation. Switching to a thermally insulating ceramic vessel produces a maximum reaction temperature of 2010 K because of the more nearly adiabatic conditions. The high reaction temperature appears to be critical to forming phase-pure AlN. Experiments with Li(3)N, instead of Ca(3)N(2), produce lower temperatures (1513 K), resulting in both Al and Al(2)O(3) impurities.

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Polyaniline nanofibers: facile synthesis and chemical sensors.

Polyaniline nanofibers with uniform diameters between 30 and 50 nm can be made in bulk quantities through a facile aqueous/organic interfacial polymerization method at ambient conditions. The nanofibers have lengths varying from 500 nm to several micrometers and form interconnected networks. Thin films made of the nanofibers have superior performance in both sensitivity and time response to vapors of acid (HCl) and base (NH3).

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