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C4F7N [2,3,3,3-tetrafluoro-2-(trifluoromethyl)propanenitrile]/CO2 gas mixtures are being developed as an eco-friendly electrical insulator to replace SF6, the most potent greenhouse industrial gaseous dielectric. However, recent studies have reported complicated and often conflicting decomposition pathways for C4F7N/CO2 gas mixtures, which has raised concerns. In this work, the decomposition characteristics of C4F7N/CO2 gas mixtures were studied comprehensively by both designed computations and experiments. Computations were performed starting from fundamental propositions of C4F7N/CO2 decompositions, which were further experimentally verified by pyrolysis, long-term thermal aging with/without catalytic materials (industrial-grade molecular sieves 4A), and electrical decomposition by spark discharge. The results of both computations and experiments suggest that in an ideal thermal decomposition, C4F7N is likely to decompose into C2F6 and small fluoronitriles first at high temperatures. The generation of C3F6 and C2N2 from C4F7N thermal decomposition at lower temperatures appears because of the catalytic effect of incompatible materials, for example, the industrial-grade molecular sieves 4A that we tested. The electron impact dissociation of C4F7N plays an important role in C4F7N electrical decomposition, leading to additional formation of distinctive small molecules of CF4 and C2N2 of low concentrations. It was pointed out based on a real arcing test in a load disconnector that the decomposition of C4F7N gas mixtures in real applications will be at a much moderate and manageable rate than what was obtained from the highly accelerated laboratory tests presented in this work. The signatures of decomposition products extracted in this study provide invaluable guidance for developing decomposition-based diagnosis and fixation of decomposition byproducts toward SF6-free power grids. [ABSTRACT FROM AUTHOR]

We demonstrate a new attractive approach for ubiquitous quantitative chemical or biological sensing when analog signals are acquired from conventional optical disk drives, and these signals are used for quantitative detection of optical changes of sensing films deposited on conventional CD and DVD optical disks. Our developed analytical model of the operation of this Lab-on-DVD system describes the optical response of sensing films deposited onto the read surface of optical disks by taking into account the practical aspects of system performance that include possible reagent leaching effects, water sampling (delivering) efficiency, and possible changes of the film morphology after water removal. By applying a screen-printing process, we demonstrated a laboratory-scale automated production of sensing films with an average thickness of ~10 [micro]m and a thickness relative standard deviation of OCIS codes: 000.1570, 120.4640, 160.5470, 230.0230.

We demonstrate an approach for multianalyte chemical identification and quantitation using a single conventional radio frequency identification (RFID) tag that has been adapted for chemical sensing. Unlike other approaches of using RFID sensors, where a special tag should be designed at a much higher cost, we utilize a conventional RFID tag and coat it with a chemically sensitive film. As an example, we demonstrate detection of several vapors of industrial, health, law enforcement, and security interest (ethanol, methanol, acetonitrile, water vapors) with a single 13.56-MHz RFID tag coated with a solid polymer electrolyte sensing film. By measuring simultaneously several parameters of the complex impedance from such an RFID sensor and applying multivariate statistical analysis methods, we were able to identify and quantify several vapors of interest. With a careful selection of the sensing film and measurement conditions, we achieved parts-per-billion vapor detection limits in air. These RFID sensors are very attractive as ubiquitous multianalyte distributed sensor networks.

Optoelectronic consumer products that are widely employed in the office and home attract attention for optical sensor applications due to (1) their cost advantage over analytical instruments produced only in small quantities, (2) robustness in operation due to the detailed manufacturability improvements, and (3) ease of operation. We demonstrate here a new approach for quantitative chemical/biochemical sensing when analog signals are acquired from conventional optical disk drives, and these signals are used for quantitative detection of optical changes of sensor films deposited on conventional CD and DVD optical disks. Because we do not alter manufacturing process of optical disks, any disk can be employed for deposition and readout of sensor films. The optical disk drives also perform their original function of reading and writing digital content to optical media because no optical modifications are introduced to obtain the analog signal. Such a sensor platform is quite universal and can be applied for chemical and biological quantitative detection, as well as for monitoring of changes of physical properties of regions deposited onto a CD or DVD (e.g., during combinatorial screening of materials). As a model example, we demonstrate the concept using chemical detection of ionic species such as [Ca.sup.2+] in liquids (e.g., blood, urine, or water). Colorimetric calcium-sensitive sensor films were deposited onto a DVD, exposed to water with different concentrations of [Ca.sup.2+], and quantified in the optical disk drive. The developed lab-on-DVD system demonstrated a 5 ppm detection limit of [Ca.sup.2+] determinations, similar or slightly better than that achieved using a conventional fiber-optic portable spectrometer. This detection limit corresponded to a 0.023 absorbance unit resolution, as determined by the measurement of the same colorimetric films with a portable spectrometer. Determinations of [Ca.sup.2+] unknowns using the lab-on-DVD system demonstrated [+ or -] 5 ppm accuracy and 2-5% relative standard deviation precision in predicting 100 ppm [Ca.sup.2+].

We demonstrate an approach for the development of chemical sensors utilizing silicon micromachined physical transducers with integrated piezoresistive readout. Originally, these transducers were developed and optimized as sensitive accelerometers for automotive applications. However, by applying a chemically responsive layer onto the transducer, we convert these transducers into chemical sensors. These transducers are attractive for chemical sensing applications for several key reasons. First, the required sensitivity of the chemical sensor can be achieved by choosing the right spring constant of the transducer. Second, the integrated piezoresistive readout of the transducer is already optimized and is very straightforward, providing a desired reproducibility in measurements, while not requiring bulky equipment. Third, chemically responsive film deposition is simple due to the ease of access to the transducer's surface. Fourth, such transducers are already available for another (automotive) application, making these sensors very cost-effective. The applicability of this approach is illustrated by the fabrication of highly sensitive C[O.sub.2] sensors. To study hysteresis effects, we selected high C[O.sub.2] concentrations (10-100% C[O.sub.2]) to provide the worst-case scenario for the sensor operation. These sensors demonstrate a hysteresis-free performance over the concentration range from 10 to 100% vol C[O.sub.2], have detection limits of 160-370 ppm of C[O.sub.2], and exhibit a relatively rapid response time, [T.sub.90] = 45 s. Importantly, we demonstrate a simple method for cancellation of vibration effects when these physical transducers, initially developed as accelerometers, are applied as chemical sensors.

Polymers are important materials for sensor, microfluidic, and other demanding applications. High-throughput screening methodology has been applied for the evaluation of the solvent resistance of a family of polycarbonate copolymers prepared from the reaction of bisphenol A (BPA), hydroquinone (HQ), and resorcinol (RS) in different solvents of practical importance, such as chloroform, tetrahydrofuran (THF), and methyl ethyl ketone (MEK). We employed a 24-channel acoustic-wave sensor system that provided previously unavailable capabilities for parallel evaluation of polymer solvent resistance. This high-throughput polymer evaluation approach assisted in construction of detailed solvent-resistance maps of polycarbonate copolymers and in determination of quantitative structure--property relationships. The best absolute solvent resistance of all studied copolymers was achieved in MEK, followed by chloroform and THF. A D-optimal mixture design was employed to explore the relationship between the copolymer compositions and their solvent resistance. The applied special cubic model for each solvent took into account the primary mixture terms such as BPA, HQ, and RS; binary interaction terms such as BPA-HQ, BPA-RS, and HQ-RS; and a ternary interaction term BPA-HQ-RS. A combination of the normal distribution of the model residuals and the very high values of adjusted [R.sup.2] (0.97-0.99) demonstrated a good quality of the model. At a HQ concentration of 40 mol %, the solvent resistance was the highest for all tested solvents, and different concentrations of BPA (40 and 60 mol %) and RS (0 and 20 mol %) did not affect the solvent resistance. Without HQ, solvent resistance was decreasing with an increase of RS and decrease of BPA. Overall, with an increase of HQ concentration from 0 to 40 mol %, the solvent resistance of BPA-HQ-RS copolymers was improved by up to 3 times in THF, by 21 times in chloroform, and by 32 times in MEK.

We demonstrate that silicone block polyimide polymers have an unusually high sensitivity to nonpolar organic vapors, including chlorinated organic solvent vapors. When 0.18-5.34-[micro]m-thick films of silicone block polyimide polymers were deposited onto 10-MHz thickness shear mode (TSM) oscillators, these films were implemented to detect parts-per-billion concentrations of trichloroethylene (TCE) with a detection sensitivity of 0.5-23.5 Hz per 500 ppb of vapor. With a film thickness of 3.4 [micro]m (91.5-kHz frequency shift upon film deposition), optimized for the minimal sensor noise of 0.04 Hz, the calculated detection limit of sensor response (S/N = 3) was 3 ppb of TCE. Detection limits for other chlorinated organic solvent vapors, such as perchloroethylene (PCE), cis-1,2-dichloroethylene (DCE), trans-1,2-DCE, 1,1-DCE, and vinyl chloride (VC) were 0.6, 6, 6, 11, and 13 ppb, respectively. Assuming only the mass-loading response when deposited onto the TSM devices, silicone block polyimide polymers have partition coefficients of over 200 000 to parts-per-billion concentrations of TCE that make them at least 100 times more sensitive than other known polymers for TCE detection. We observed that unlike conventional polyimides, water sensitivity of the new hybrid polyimides is suppressed because of the silicone soft block. Water sensitivity is comparable with the sensor response to nonpolar organic vapors. The high sensitivity and long-term stability of these sensor materials make them attractive for ultrasensitive practical sensors.

A new general approach for rapid assessment of polymerization catalysts is introduced. Native fluorescence emission of solid polymers is measured directly in combinatorial 96-microreactor arrays and polymers produced in a laboratory-scale validation reactor. Fluorescence features collected with a CCD-based spectrofluorometer are correlated with chemical properties of interest such as polymer molecular weight, amount of branching, and catalyst selectivity. The approach is illustrated by screening of selectivity of melt polymerization catalysts used in synthesis of an aromatic bisphenol A polycarbonate. Selectivity of catalysts correlated with the ratio of fluorescence intensities at 400 and 500 nm at 340-nm excitation. The relative standard deviation (RSD) in spectroscopic serial measurements was 1-12.5%. This spread included instrument variability ([less than or equal to] 1% RSD) and sample inhomogeneity. Parallel quantitative screening of catalyst selectivity in combinatorial 96-microreactor arrays was performed as a two-wavelength ratiometric fluorescence imaging through 400- and 500-nm interference filters and showed a good correlation ([R.sup.2] = 0.994) with serial screening. Our approach is an attractive alternative to traditional separation-based techniques if speed and nondestructive nature of analysis are critical and when the high cross-linking or solvent resistance of polymers complicates traditional analysis.

An automated analytical system has been implemented for the high-throughput optimization of processing conditions such as curing parameters in fabrication of UV-cured automotive organic protective coatings. Selection of optimum process conditions of combinatorial arrays of coatings is essential to correlate the high-throughput screening and conventional processes and to achieve the desired physical properties of coatings. For monitoring of curing conditions of each coating in the array, a viscosity-sensitive fluorophore 4,4'-bis(2-benzoxazolyi)stilbene was incorporated into coating formulations. This fluorescence tagging approach permitted us to combine a gradient temperature heater and a UV curing system with the full capabilities of our high-throughput screening system, including generation of spectroscopic data and its analysis. This investigation demonstrated the possibility of rapid decoupling of temperature and radiation effects in curing of UV-curable coating formulations by using multiple coatings and process conditions at once. While the system described here was implemented for high-throughput optimization of temperature conditions of radiation curing of arrays of organic protective coatings for automotive applications, this system can be further applied for a variety of other applications where optimization of process parameters can be studied in situ or off-line using optical spectroscopic tools.

Design, validation, and implementation of an optical spectroscopic system for high-throughput analysis of combinatorially developed protective organic coatings are reported. Our approach replaces labor-intensive coating evaluation steps with an automated system that rapidly analyzes 8 x 6 arrays of coating elements that are discretely deposited on a single plastic substrate. Each coating element of the library is 10 mm in diameter and 2-5 [micro]m thick. Performance of coatings is evaluated with respect to their resistance to wear abrasion because this parameter is one of the primary considerations in end-use applications. Upon testing, the coating materials undergo changes that are impossible to quantitatively predict using existing knowledge. Coatings are abraded using industry-accepted abrasion test methods at a single or multiple abrasion conditions followed by the high-throughput analysis of abrasion-induced light scatter. The developed automated system is optimized for the analysis of diffusively scattered light that corresponds to 0-30% haze. System precision of 0.1-2.5% relative standard deviation provides capability for the reliable ranking of coatings performance. Although the system was implemented for high-throughput screening of combinatorially developed organic protective coatings for automotive applications, it can be applied for a variety of other applications for which materials ranking can be achieved using optical spectroscopic tools.