Annealing Would Improve beta" - Alumina Solid Electrolyte

A pre-operational annealing process is under investigation as a potential means of preventing a sudden reduction of ionic conductivity in a Beta"-alumina solid electrolyte (BASE) during use. On the basis of tests, the sudden reduction of ionic conductivity, followed by a slow recovery, has been found to occur during testing of the solid electrolyte and electrode components of an alkali metal thermal-to-electric converter (AMTEC) cell. At this time, high-temperature tests of limited duration have indicated the superiority of the treated BASE, but reproducible tests over thousands of hours are necessary to confirm that microcracking has been eliminated. The ionic conductivity of the treated BASE is also measured to be higher than untreated BASE at 1,073 K in low-pressure sodium vapor. Microcracking resulting in loss of conductivity was not observed with treated BASE in one high-temperature experiment, but this result must be duplicated over very long testing times to be sure of the effect. Shorter annealing times (10 to 20 hours) were found to result in significantly less loss of mass; it may be necessary for the packed powder mixture to evolve some Na2O before the Na2O can leave the ceramic

Detecting Airborne Mercury by Use of Gold Nanowires

Like the palladium chloride (PdCl2) films described in the immediately preceding article, gold nanowire sensors have been found to be useful for detecting airborne elemental mercury at concentrations on the order of parts per billion (ppb). Also like the PdCl2 films, gold nanowire sensors can be regenerated under conditions much milder than those necessary for regeneration of gold films that have been used as airborne-Hg sensors. The interest in nanowire sensors in general is prompted by the expectation that nanowires of a given material covering a given surface may exhibit greater sensitivity than does a film of the same material because nanowires have a greater surface area. In preparation for experiments to demonstrate this sensor concept, sensors were fabricated by depositing gold nanowires, variously, on microhotplate or microarray sensor substrates. In the experiments, the electrical resistances were measured while the sensors were exposed to air at a temperature of 25 C and relative humidity of about 30 percent containing mercury at various concentrations from 2 to 70 ppb (see figure). The results of this and other experiments have been interpreted as signifying that sensors of this type can detect mercury at ppb concentrations in room-temperature air and can be regenerated by exposure to clean flowing air at temperatures <40 C

Gold-on-Polymer-Based Sensing Films for Detection of Organic and Inorganic Analytes in the Air

A document discusses gold-on-polymer as one of the novel sensor types developed for part of the sensor development task. Standard polymer-carbon composite sensors used in the JPL Electronic Nose (ENose) have been modified by evaporating 15 nm of metallic gold on the surface. These sensors have been shown to respond to alcohols, aromatics, ammonia, sulfur dioxide, and elemental mercury in the parts-per-million and parts-per-billion concentration ranges in humidified air. The results have shown good sensitivity of these films operating under mild conditions (operating temperatures 23-28 C and regeneration temperature up to 40 C). This unique sensor combines the diversity of polymer sensors for chemical sensing with their response to a wide variety of analytes with the specificity of a gold sensor that shows strong reaction/binding with selected analyte types, such as mercury or sulfur

Mo/Ti Diffusion Bonding for Making Thermoelectric Devices

An all-solid-state diffusion bonding process that exploits the eutectoid reaction between molybdenum and titanium has been developed for use in fabricating thermoelectric devices based on skutterudite compounds. In essence, the process is one of heating a flat piece of pure titanium in contact with a flat piece of pure molybdenum to a temperature of about 700 C while pushing the pieces together with a slight pressure [a few psi (of the order of 10 kPa)]. The process exploits the energy of mixing of these two metals to form a strong bond between them. These two metals were selected partly because the bonds formed between them are free of brittle intermetallic phases and are mechanically and chemically stable at high temperatures. The process is a solution of the problem of bonding hot-side metallic interconnections (denoted hot shoes in thermoelectric jargon) to titanium-terminated skutterudite n and p legs during the course of fabrication of a unicouple, which is the basic unit cell of a thermoelectric device (see figure). The hot-side operating temperature required for a skutterudite thermoelectric device is 700 C. This temperature precludes the use of brazing to attach the hot shoe; because brazing compounds melt at lower temperatures, the hot shoe would become detached during operation. Moreover, the decomposition temperature of one of the skutterudite compounds is 762 C; this places an upper limit on the temperature used in bonding the hot shoe. Molybdenum was selected as the interconnection metal because the eutectoid reaction between it and the titanium at the ends of the p and n legs has characteristics that are well suited for this application. In addition to being suitable for use in the present bonding process, molybdenum has high electrical and thermal conductivity and excellent thermal stability - characteristics that are desired for hot shoes of thermoelectric devices. The process takes advantage of the chemical potential energy of mixing between molybdenum and titanium. These metals have a strong affinity for each other. They are almost completely soluble in each other and remain in the solid state at temperatures above the eutectoid temperature of 695 C. As a result, bonds formed by interdiffusion of molybdenum and titanium are mechanically stable at and well above the original bonding temperature of about 700 C. Inasmuch as the bonds are made at approximately the operating temperature, thermomechanical stresses associated with differences in thermal expansion are minimized

Detecting Airborne Mercury by Use of Palladium Chloride

Palladium chloride films have been found to be useful as alternatives to the gold films heretofore used to detect airborne elemental mercury at concentrations of the order of parts per billion (ppb). Somewhat more specifically, when suitably prepared palladium chloride films are exposed to parts-per-billion or larger concentrations of airborne mercury, their electrical resistances change by amounts large enough to be easily measurable. Because airborne mercury adversely affects health, it is desirable to be able to detect it with high sensitivity, especially in enclosed environments in which there is a risk of leakage of mercury from lamps or other equipment. The detection of mercury by use of gold films involves the formation of gold/mercury amalgam. Gold films offer adequate sensitivity for detection of airborne mercury and could easily be integrated into an electronic-nose system designed to operate in the temperature range of 23 to 28 C. Unfortunately, in order to regenerate a gold-film mercury sensor, one must heat it to a temperature of 200 C for several minutes in clean flowing air. In preparation for an experiment to demonstrate the present sensor concept, palladium chloride was deposited from an aqueous solution onto sets of gold electrodes and sintered in air to form a film. Then while using the gold electrodes to measure the electrical resistance of the films, the films were exposed, at a temperature of 25 C, to humidified air containing mercury at various concentrations from 0 to 35 ppb (see figure). The results of this and other experiments have been interpreted as signifying that sensors of this type can detect mercury in room-temperature air at concentrations of at least 2.5 ppb and can readily be regenerated at temperatures <40 C

Detection of Carbon Monoxide Using Polymer-Composite Films with a Porphyrin-Functionalized Polypyrrole

Post-fire air constituents that are of interest to NASA include CO and some acid gases (HCl and HCN). CO is an important analyte to be able to sense in human habitats since it is a marker for both prefire detection and post-fire cleanup. The need exists for a sensor that can be incorporated into an existing sensing array architecture. The CO sensor needs to be a low-power chemiresistor that operates at room temperature; the sensor fabrication techniques must be compatible with ceramic substrates. Early work on the JPL ElectronicNose indicated that some of the existing polymer-carbon black sensors might be suitable. In addition, the CO sensor based on polypyrrole functionalized with iron porphyrin was demonstrated to be a promising sensor that could meet the requirements. First, pyrrole was polymerized in a ferric chloride/iron porphyrin solution in methanol. The iron porphyrin is 5, 10, 15, 20-tetraphenyl-21H, 23Hporphine iron (III) chloride. This creates a polypyrrole that is functionalized with the porphyrin. After synthesis, the polymer is dried in an oven. Sensors were made from the functionalized polypyrrole by binding it with a small amount of polyethylene oxide (600 MW). This composite made films that were too resistive to be measured in the device. Subsequently, carbon black was added to the composite to bring the sensing film resistivity within a measurable range. A suspension was created in methanol using the functionalized polypyrrole (90% by weight), polyethylene oxide (600,000 MW, 5% by weight), and carbon black (5% by weight). The sensing films were then deposited, like the polymer-carbon black sensors. After deposition, the substrates were dried in a vacuum oven for four hours at 60 C. These sensors showed good response to CO at concentrations over 100 ppm. While the sensor is based on a functionalized pyrrole, the actual composite is more robust and flexible. A polymer binder was added to help keep the sensor material from delaminating from the electrodes, and carbon was added to improve the conductivity of the material

Stability Enhancement of Polymeric Sensing Films Using Fillers

Experiments have shown the stability enhancement of polymeric sensing films on mixing the polymer with colloidal filler particles (submicron-sized) of carbon black, silver, titanium dioxide, and fumed silicon dioxide. The polymer films are candidates for potential use as sensing media in micro/nano chemical sensor devices. The need for stability enhancement of polymer sensing films arises because such films have been found to exhibit unpredictable changes in sensing activity over time, which could result in a possible failure of the sensor device. The changes in the physical properties of a polymer sensing film caused by the sorption of a target molecule can be measured by any of several established transduction techniques: electrochemical, optical, calorimetric, or piezoelectric, for example. The transduction technique used in the current polymer stability experiments is based on piezoelectric principles using a quartz-crystal microbalance (QCM). The surface of the QCM is coated with the polymer, and the mass uptake by the polymer film causes a change in the oscillating frequency of the quartz crystal. The polymer used for the current study is ethyl cellulose. The polymer/ polymer composite solutions were prepared in 1,3 dioxolane solvent. The filler concentration was fixed at 10 weight percent for the composites. The polymer or polymer composite solutions were cast on the quartz crystal having a fundamental frequency of about 6 MHz. The coated crystal was subjected to a multistage drying process to remove all measurable traces of the solvent. In each experiment, the frequency of oscillation was measured while the QCM was exposed to clean, dry, flowing air for about 30 minutes, then to air containing a known concentration of isopropanol for about 30 minutes, then again to clean dry air for about 30 minutes, and so forth. This cycle of measurements for varying isopropanol concentrations was repeated at intervals for several months. The figure depicts some of the sensing film stability results for ethyl cellulose polymer, ethyl cellulose-carbon black, and ethyl cellulose-silicon dioxide composite systems. An ethyl cellulose film exhibited a marked decline in response in the first few months of study and settled to a steady average response after about four months. However, response varied widely around the average response for ethyl cellulose film. In contrast, ethyl cellulose- carbon black and ethyl cellulose-silicon dioxide composites also declined in the early months, but showed more repeatable sensing film activity after the initial decline. Similar trends were observed in experiments for ethyl cellulose-titanium dioxide and ethyl cellulose-silver composites

Special Polymer/Carbon Composite Films for Detecting SO2

A family of polymer/carbon films has been developed for use as sensory films in electronic noses for detecting SO2 gas at concentrations as low as 1 part per million (ppm). Most previously reported SO2 sensors cannot detect SO2 at concentrations below tens of ppm; only a few can detect SO2 at 1 ppm. Most of the sensory materials used in those sensors (especially inorganic ones that include solid oxide electrolytes, metal oxides, and cadmium sulfide) must be used under relatively harsh conditions that include operation and regeneration at temperatures greater than 100 C. In contrast, the present films can be used to detect 1 ppm of SO2 at typical opening temperatures between 28 and 32 C and can be regenerated at temperatures between 36 and 40 C. The basic concept of making sensing films from polymer/carbon composites is not new. The novelty of the present family of polymer/carbon composites lies in formulating the polymer components of these composites specifically to optimize their properties for detecting SO2. First-principles quantum-mechanical calculations of the energies of binding of SO2 molecules to various polymer functionalities are used as a guide for selecting polymers and understanding the role of polymer functionalities in sensing. The polymer used in the polymer-carbon composite is a copolymer of styrene derivative units with vinyl pyridine or substituted vinyl pyridine derivative units. To make a substituted vinyl pyridine for use in synthesizing such a polymer, poly(2-vinyl pyridine) that has been dissolved in methanol is reacted with 3-chloropropylamine that has been dissolved in a solution of methanol. The methanol is then removed to obtain the copolymer. Later, the copolymer can be dissolved in an appropriate solvent with a suspension of carbon black to obtain a mixture that can be cast and then dried to obtain a sensory film

Effects of Temperature on Polymer/Carbon Chemical Sensors

Experiments were conducted on the effects of temperature, polymer molecular weight, and carbon loading on the electrical resistances of polymer/carbon-black composite films. The experiment were performed in a continuing effort to develop such films as part of the JPL Electronic Nose (ENose), that would be used to detect, identify, and quantify parts-per-million (ppm) concentration levels of airborne chemicals in the space shuttle/space station environments. The polymers used in this study were three formulations of poly(ethylene oxide) [PEO] that had molecular weights of 20 kilodaltons, 600 kilodaltons, and 1 megadalton, respectively. The results of one set of experiments showed a correlation between the polymer molecular weight and the percolation threshold. In a second set of experiments, differences among the temperature dependences of resistance were observed for different carbon loadings; these differences could be explained by a change in the conduction mechanism. In a third set of experiments, the responses of six different polymer/carbon composite sensors to three analytes (water vapor, methanol, methane) were measured as a function of temperature (28 to 36 C). For a given concentration of each analyte, the response of each sensor decreased with increasing temperature, in a manner different from those of the other sensors

System for detecting and estimating concentrations of gas or liquid analytes

A sensor system for detecting and estimating concentrations of various gas or liquid analytes. In an embodiment, the resistances of a set of sensors are measured to provide a set of responses over time where the resistances are indicative of gas or liquid sorption, depending upon the sensors. A concentration vector for the analytes is estimated by satisfying a criterion of goodness using the set of responses. Other embodiments are described and claimed