Variation of the partial thermodynamic properties of oxygen with composition in YBa2Cu3O7−δ

The variation of equilibrium oxygen potential with oxygen concentration inYBa 2Cu3O7-δhas been measured in the temperature range of 773 to 1223 K. For temperatures up to 1073 K, the oxygen content of theYBa 2Cu3O7-δsample, held in a stabilized-zirconia crucible, was altered by coulometric titration. The compound was in contact with the electrolyte, permitting direct exchange of oxygen ions. For measurements above 1073 K, the oxide was contained in a magnesia crucible placed inside a closed silica tube. The oxygen potential in the gas phase above the 123 compound was controlled and measured by a solid-state cell based on yttria-stabilized zirconia, which served both as a pump and sensor. Pure oxygen at a pressure of 1.01 × 105 Pa was used as the reference electrode. The oxygen pressure over the sample was varied from 10-1 to 105 Pa. The oxygen concentrations of the sample equilibrated with pure oxygen at 1.01 × 105 Pa at different temperatures were determined after quenching in liquid nitrogen by hydrogen reduction at 1223 K. The plot of chemical potential of oxygen as a function of oxygen non-stoichiometry shows an inflexion at δ ∼ 0.375 at 873 K. Data at 773 K indicate tendency for phase separation at lower temperatures. The partial enthalpy and entropy of oxygen derived from the temperature dependence of electromotive force (emf ) exhibit variation with composition. The partial enthalpy for °= 0.3, 0.4, and 0.5 also appears to be temperature dependent. The results are discussed in comparison with the data reported in the literature. An expression for the integral free energy of formation of YBa2Cu3O6.5 is evaluated based on measurements reported in the literature. By integration of the partial Gibbs’ energy of oxygen obtained in this study, the variation of integral property with oxygen concentration is obtained at 873 K.

Design, Development and Calibration of HTS Wire Based LOX Level Sensor Probe

For space applications, the weight of the liquid level sensors are of major concern as they affect the payload fraction and hence the cost. An attempt is made to design and test a light weight High Temperature Superconductor (HTS) wire based liquid level sensor for Liquid Oxygen (LOX) tank used in the cryostage of the spacecraft. The total resistance value measured of the HTS wire is inversely proportional to the liquid level. A HTS wire (SF12100) of 12mm width and 2.76m length without copper stabilizer has been used in the level sensor. The developed HTS wire based LOX level sensor is calibrated against a discrete diode array type level sensor. Liquid Nitrogen (LN2) and LOX has been used as cryogenic fluid for the calibration purpose. The automatic data logging for the system has been done using LabVIEW11. The net weight of the developed sensor is less than 1 kg.

A novel, sensitive potentiometric hydrocarbon sensor for high-vacuum applications.

A potentiometric device based on interfacing a solid electrolyte oxygen ion conductor with a thin platinum film acts as a robust, reproducible sensor for the detection of hydrocarbons in high- or ultrahigh-vacuum environments. Sensitivities in the order of approximately 5 x 10(-10) mbar are achievable under open circuit conditions, with good selectivity for discrimination between n-butane on one hand and toluene, n-octane, n-hexane, and 1-butene on the other hand. The sensor's sensitivity may be tuned by operating under constant current (closed circuit) conditions; injection of anodic current is also a very effective means of restoring a clean sensing surface at any desired point. XPS data and potentiometric measurements confirm the proposed mode of sensing action: the steady-state coverage of Oa, which sets the potential of the Pt sensing electrode, is determined by the partial pressure and dissociative sticking probability of the impinging hydrocarbon. The principles established here provide the basis for a viable, inherently flexible, and promising means for the sensitive and selective detection of hydrocarbons under demanding conditions.

A Simple and Inexpensive Method for Fabrication of Ultramicroelectrode Array and Its Application for the Detection of Dissolved Oxygen

Herein, we report a simple and inexpensive way for fabrication of ultra microelectrode arrays (UMEAs) and the relative characterization methods. The fabrication of UMEAs involves only a few steps of handwork. Since only metal wires and epoxy are used through the fabrication process, it is supposed to be a quite straightforward method for preparing UMEAs. A dissolved oxygen (DO) sensor based on UMEAs was constructed.

Double-template synthesis of platinum nanomaterials for oxygen reduction

Gas bubble dynamic template, a new green and promising template, can be used to prepare nanostructured materials with different shapes from electrochemical deposition processes. Different morphological platinum nanomaterials have been synthesized by the replacement reaction of the deposited copper nanomaterials which were obtained under negative potential along with H-2 evolution (dynamic template) at a glassy carbon electrode. Scanning electron microscopy, X-ray photoelectron spectroscopy, X-ray diffraction, and electrochemical methods were adopted to characterize their structures and properties. The nanomaterials platinum exhibited excellent catalytic activity toward oxygen reduction. The results demonstrated that the strategy is a simple, cost-effective, and potent method to prepare platinum nanomaterials.

Development and assessment of new sensor systems in food packaging applications

The use of optical sensor technology for non-invasive determination of key quality pack parameters improved package/product quality. This technology can be used for optimization of packaging processes, improvement of product shelf-life and maintenance of quality. In recent years, there has been a major focus on O2 and CO2 sensor development as these are key gases used in modified atmosphere packaging (MAP) of food. The first and second experimental chapters (chapter 2 and 3) describe the development of O2, pH and CO2 solid state sensors and its (potential) use for food packaging applications. A dual-analyte sensor for dissolved O2 and pH with one bi-functional reporter dye (meso-substituted Pd- or Ptporphyrin) embedded in plasticized PVC membrane was developed in chapter 2. The developed CO2 sensor in chapter 3 was comprised of a phosphorescent reporter dye Pt(II)- tetrakis(pentafluorophenyl) porphyrin (PtTFPP) and a colourimetric pH indicator α-naphtholphthalein (NP) incorporated in a plastic matrix together with a phase transfer agent tetraoctyl- or cetyltrimethylammonium hydroxide (TOA-OH or CTA-OH). The third experimental chapter, chapter 4, described the development of liquid O2 sensors for rapid microbiological determination which are important for improvement and assurance of food safety systems. This automated screening assay produced characteristic profiles with a sharp increase in fluorescence above the baseline level at a certain threshold time (TT) which can be correlated with their initial microbial load and was applied to various raw fish and horticultural samples. Chapter 5, the fourth experimental chapter, reported upon the successful application of developed O2 and CO2 sensors for quality assessment of MAP mushrooms during storage for 7 days at 4°C.

Use of oxygen sensors for the non destructive measurement of oxygen in packaged food and beverage products and its impact on product quality and shelf life

The principal objective of this thesis was to investigate the ability of reversible optical O2 sensors to be incorporated into food/beverage packaging systems to continuously monitor O2 levels in a non-destructive manner immediately postpackaging and over time. Residual levels of O2 present in packs can negatively affect product quality and subsequently, product shelf-life, especially for O2-sensitive foods/beverages. Therefore, the ability of O2 sensors to continuously monitor O2 levels present within food/beverage packages was considered commercially relevant in terms of identifying the consequences of residual O2 on product safety and quality over time. Research commenced with the development of a novel range of O2 sensors based on phosphorescent platinum and palladium octaethylporphyrin-ketones (OEPk) in nano-porous high density polyethylene (HDPE), polypropylene (PP) polytetrafluoroethylene (PTFE) polymer supports. Sensors were calibrated over a temperature range of -10°C to +40°C and deemed suitable for food and beverage packaging applications. This sensor technology was used and demonstrated itself effective in determining failures in packaging containment. This was clearly demonstrated in the packaging of cheese string products. The sensor technology was also assessed across a wide range of packaged products; beer, ready-to-eat salad products, bread and convenience-style, muscle-based processed food products. The O2 sensor technology performed extremely well within all packaging systems. The sensor technology adequately detected O2 levels in; beer bottles prior to and following pasteurisation, modified atmosphere (MA) packs of ready-to-eat salad packs as respiration progressed during product storage and MA packs of bread and convenience-style muscle-based products as mycological growth occurred in food packs over time in the presence and absence of ethanol emitters. The use of the technology, in conjunction with standard food quality assessment techniques, showed remarkable usefulness in determining the impact of actual levels of O2 on specific quality attributes. The O2 sensing probe was modified, miniaturised and automated to screen for the determination of total aerobic viable counts (TVC) in several fish species samples. The test showed good correlation with conventional TVC test (ISO:4833:2003), analytical performance and ruggedness with respect to variation of key assay parameters (probe concentration and pipetting volume). Overall, the respirometric fish TVC test was simple to use, possessed a dynamic microbial range (104-107 cfu/g sample), had an accuracy of +/- one log(cfu/g sample) and was rapid. Its ability to assess highly perishable products such as fish for total microbial growth in <12 hr demonstrates commercial potential.

Bioluminescence imaging of glucose in tissue surrounding polyurethane and glucose sensor implants.

BACKGROUND: The bioluminescence technique was used to quantify the local glucose concentration in the tissue surrounding subcutaneously implanted polyurethane material and surrounding glucose sensors. In addition, some implants were coated with a single layer of adipose-derived stromal cells (ASCs) because these cells improve the wound-healing response around biomaterials. METHODS: Control and ASC-coated implants were implanted subcutaneously in rats for 1 or 8 weeks (polyurethane) or for 1 week only (glucose sensors). Tissue biopsies adjacent to the implant were immediately frozen at the time of explant. Cryosections were assayed for glucose concentration profile using the bioluminescence technique. RESULTS: For the polyurethane samples, no significant differences in glucose concentration within 100 μm of the implant surface were found between bare and ASC-coated implants at 1 or 8 weeks. A glucose concentration gradient was demonstrated around the glucose sensors. For all sensors, the minimum glucose concentration of approximately 4 mM was found at the implant surface and increased with distance from the sensor surface until the glucose concentration peaked at approximately 7 mM at 100 μm. Then the glucose concentration decreased to 5.5-6.5 mM more than 100 μmm from the surface. CONCLUSIONS: The ASC attachment to polyurethane and to glucose sensors did not change the glucose profiles in the tissue surrounding the implants. Although most glucose sensors incorporate a diffusion barrier to reduce the gradient of glucose and oxygen in the tissue, it is typically assumed that there is no steep glucose gradient around the sensors. However, a glucose gradient was observed around the sensors. A more complete understanding of glucose transport and concentration gradients around sensors is critical.

Oxygen indicators and intelligent inks for packaging food

The detection of oxygen using optical sensors is of increasing interest, especially in modified atmosphere food packaging (MAP), in which the package, usually containing food, is flushed with a gas, such as carbon dioxide or nitrogen. This tutorial review examines the ideal properties of an oxygen optical sensor for MAP and compares them with those developed to date, including the most recent advances. The basic technologies underpinning the different indicator types are described, examples given and their potential for application in MAP assessed. This tutorial review should be of interest to the MAP industry and researchers in optical sensors and oxygen sensing.

Fluorescence-based thin plastic film ion-pair sensors for oxygen

A general method of preparation of thin-film sensors for O-2, incorporating the dye ion-pair tris(4,7-diphenyl-1,10-phenanthroline) rutheninm(II) ditetraphenylborate, in a variety of different thin film polymer/plasticizer matrices is described, The sensitivity of the sensor depends upon the nature of the polymer matrix and plasticizer, A detailed study of one of these systems utilising the polymer poly(methyl methacrylate), PMMA, is reported. The sensitivity of this O-2 sensor depends markedly upon the plasticizer concentration and is largely independent of temperature (24,5-52.5 degrees C) and age (up to 30 d), When exposed to an alternating atmosphere of O-2 and N-2, a typical oxygen film sensor in PMMA exhibits a 0-90% response and recovery time of 0.4 and 4.5 s, respectively.

Novel titania sol-gel derived film for luminescence-based oxygen sensing.

A novel method for the preparation of titania sol–gel derived oxygen sensors based on the ruthenium(II) dye, [Ru(bpy)3]2+, is described. A titania sol–gel paste film was cast onto microscope slides, and the dye ion-paired to the deprotonated, hydroxylated groups on the film's surface from an aqueous solution of the dye at pH 11. The resulting sensor film is extremely oxygen sensitive, with a PO2 (S = 1/2) value (i.e. the partial pressure of oxygen required in order to reduce the original, oxygen free, luminescence intensity by 50%) of 0.011 atm. The sensor undergoes 95% response to oxygen in 4 s, and shows 95% recovery of its luminescence in argon within 7 s.

Absorption coefficient of particulate matter on the south-west coast of Europe: a contribution to the validation of the MERIS-Medium Resolution Imaging Spectrometer sensor

Dissolved oxygen (DO) is one of the most important environmental variables of water quality, especially for marine life. Consequently, oxygen is one of the Chemical Quality Elements required for the implementation of European Union Water Framework Directive. This study uses the example of the Ria Formosa, a meso-tidal lagoon on the south coast of Portugal to demonstrate how monitoring of water quality for coastal waters must be well designed to identify symptoms of episodic hypoxia. New data from the western end of the Ria Formosa were compared to values in a database of historical data and in the published literature to identify long-term trends. The dissolved oxygen concentration values in the database and in the literature were generally higher than those found in this study, where episodic hypoxia was observed during the summer. Analysis of the database showed that the discrepancy was probably related with the time and the sites where the samples had been collected, rather than a long-term trend. The most problematic situations were within the inner lagoon near the city of Faro, where episodic hypoxia (<2 mg dm3 DO) occurred regularly in the early morning. These results emphasise the need for a balanced sampling strategy for oxygen monitoring which includes all periods of the day and night, as well as a representative range of sites throughout the lagoon. Such a strategy would provide adequate data to apply management measures to reduce the risk of more persistent hypoxia that would impact on the ecological, important natural resource. economic and leisure uses of this important natural resource.

Electrochemical DNA-sensor for evaluation of total antioxidant capacity of flavours and flavoured waters using superoxide radical damage

In this paper, a biosensor based on a glassy carbon electrode (GCE) was used for the evaluation of the total antioxidant capacity (TAC) of flavours and flavoured waters. This biosensor was constructed by immobilising purine bases, guanine and adenine, on a GCE. Square wave voltammetry (SWV) was selected for the development of this methodology. Damage caused by the reactive oxygen species (ROS), superoxide radical (O2·−), generated by the xanthine/xanthine oxidase (XOD) system on the DNA-biosensor was evaluated. DNA-biosensor encountered with oxidative lesion when it was in contact with the O2·−. There was less oxidative damage when reactive antioxidants were added. The antioxidants used in this work were ascorbic acid, gallic acid, caffeic acid, coumaric acid and resveratrol. These antioxidants are capable of scavenging the superoxide radical and therefore protect the purine bases immobilized on the GCE surface. The results demonstrated that the DNA-based biosensor is suitable for the rapid assess of TAC in beverages.

Assessing the sources and magnitude of diurnal nitrate variability in the San Joaquin River (California) with an in-situ optical nitrate sensor and dual nitrate isotopes

We investigated diurnal nitrate (NO3-) concentration variability in the San Joaquin River using an in situ optical NO3- sensor and discrete sampling during a 5-day summer period characterized by high algal productivity. Dual NO3- isotopes (delta N-15(NO3) and delta O-18(NO3)) and dissolved oxygen isotopes (delta O-18(DO)) were measured over 2 days to assess NO3- sources and biogeochemical controls over diurnal time-scales. Concerted temporal patterns of dissolved oxygen (DO) concentrations and delta O-18(DO) were consistent with photosynthesis, respiration and atmospheric O-2 exchange, providing evidence of diurnal biological processes independent of river discharge. Surface water NO3- concentrations varied by up to 22% over a single diurnal cycle and up to 31% over the 5-day study, but did not reveal concerted diurnal patterns at a frequency comparable to DO concentrations. The decoupling of delta N-15(NO3) and delta O-18(NO3) isotopes suggests that algal assimilation and denitrification are not major processes controlling diurnal NO3- variability in the San Joaquin River during the study. The lack of a clear explanation for NO3- variability likely reflects a combination of riverine biological processes and time-varying physical transport of NO3- from upstream agricultural drains to the mainstem San Joaquin River. The application of an in situ optical NO3- sensor along with discrete samples provides a view into the fine temporal structure of hydrochemical data and may allow for greater accuracy in pollution assessment.

Ag dopedWO(3)-based powder sensor for the detection of NO gas in air

WO3-based materials as sensors for the monitor of environmental gases such as NO2 (NO + NO2) have been rapidly developed for various potential applications (stationary and mobile uses). It has been reported that these materials are highly sensitive to NOx with the sensitivity further enhanced by adding precious group metals (PGM such as Pt, Pd, Au, etc.). However, there has been limited work in revealing the sensing mechanism for these gases over the WO3-based sensors. In particular, the role of promoter is not yet clear though speculations on their catalytic, electronic and structural effects have been made in the past. In parallel to these PGM promoters here we report,for the first time, that Ag promotion can also enhance WO3 sensitivity significantly. In addition, this promotion decreases the optimum sensor temperature of 300 degreesC for Most WO3-based sensors, to below 200 degreesC. Characterizations (XRD, TEM, and impedance measurement) reveal that there is no significant bulk structure change nor particle size alteration in the WO3 phases during the NO exposure. However, it is found that the Ag doping creates a high concentration of oxygen vacancies in form of coordinated crystallographic shear (CS) planes onto the underneath WO3. It is thus proposed that the Ag particle facilitates the oxidative conversion of NO to NO2 followed by a subsequent NO2 adsorption on the defective WO, sites created at the Ag-WO3 interface; hence, accounting for the high molecular sensitivity. (C) 2002 Elsevier Science B.V. All rights reserved.