Metal-polymer composite sensors for volatile organic compounds: Part 1. Flow-through chemi-resistors

A new type of chemi-resistor based on a novel metal-polymer composite is described. The composite contains nickel particles with sharp nano-scale surface features, which are intimately coated by the polymer matrix so that they do not come into direct physical contact. No conductive chains of filler particles are formed even at loadings above the percolation threshold and the composite is intrinsically insulating. However, when subjected to compression the composite becomes conductive, with sample resistance falling from ≥ 1012 Ω to < 0.01 Ω. The composite can be formed into insulating granules, which display similar properties to the bulk form. A bed of granules compressed between permeable frits provides a porous structure with a start resistance set by the degree of compression while the granules are free to swell when exposed to volatile organic compounds (VOCs). The granular bed presents a large surface area for the adsorption of VOCs from the gas stream flowing through it. The response of this system to a variety of vapours has been studied for two different sizes of the granular bed and for different matrix polymers. Large responses, ΔR/R0 ≥ 10^7, are observed when saturated vapours are passed through the chemi-resistor. Rapid response allows real time sensing of VOCs and the initial state is recovered in a few seconds by purging with an inert gas stream. The variation in response as a function of VOC concentration is determined.

An investigation of the kinetics of CO 2 uptake by a synthetic calcium based sorbent

This study examines the kinetics of carbonation by CO 2 at temperatures of ca. 750°C of a synthetic sorbent composed of 15wt% mayenite (Ca 12Al 14O 33) and CaO, designated HA-85-850, and draws comparisons with the carbonation of a calcined limestone. In-situ XRD has verified the inertness of mayenite, which neither interacts with the active CaO nor does it significantly alter the CaO carbonation-calcination equilibrium. An overlapping grain model was developed to predict the rate and extent of carbonation of HA-85-850 and limestone. In the model, the initial microstructure of the sorbent was defined by a discretised grain size distribution, assuming spherical grains. The initial input to the model - the size distribution of grains - was a fitted parameter, which was in good agreement with measurements made with mercury porosimetry and by the analysis of SEM images of sectioned particles. It was found that the randomly overlapping spherical grain assumption offered great simplicity to the model, despite its approximation to the actual porous structure within a particle. The model was able to predict the performance of the materials well and, particularly, was able to account for changes in rate and extent of reaction as the structure evolved after various numbers of cycles of calcination and carbonation. © 2011 Elsevier Ltd.

Biomimetic calcium carbonate-gelatin composites as a model system for eggshell mineralization

The composite nature of mineralized natural materials is achieved through both the microstructural inclusion of an organic component and an overall microstructure that is controlled by templating onto organic macromolecules. A modification of an existing laboratory technique is developed for the codeposition of a CaCO3-gelatin composite with a controllable organic content. First, calibration curves are developed to determine the organic content of a CaCO3-gelatin composite from infrared spectra. Second, a CaCO3-gelatin composite is deposited on either glass coverslips or demineralized eggshell membranes using an automated alternating soaking process. Electron microscopy images and use of the infrared spectra calibration curves show that by altering the amount of gelatin in the ionic growth solutions, the final organic component of the mineral can be regulated over the range of 1-10%, similar to that of natural eggshell. © 2012 Materials Research Societ.

Spray drying: An alternative synthesis method for polycationic oxide compounds

Synthesis of polycationic compounds by the spray-drying technique is an interesting alternative in the domain of aqueous precursor synthesis methods. Spray drying yields high quality samples with good reproducibility. The possibility of scaling up for production of large quantities with fast processing time is well established by the commercial availability of powders of various compositions. In this paper, we have discussed the advantages and limitations of this method and demonstrated its interest by synthesizing a few polycationic compounds selected for their attractive properties of thermoelectricity [Bi1.68Ca2Co1.69O 8, La0.95A0.05CoO3 (A=Ca, Sr, Ba)] or magnetoresistance [La0.70A0.30MnO3 (A=Sr, Ba)]. We have confirmed the quality of these samples by reporting their structure, magnetic and transport properties. © 2010 Elsevier Ltd All rights reserved.

LiMn2-xTixO4 spinel-type compounds (x ≤ 1): Structural, electrical and magnetic properties

LiMn2-xTixO4 compounds with 0 ≤ x ≤ 1 were prepared by solid state reaction and Pechini technique. Powder X-ray diffraction showed that all samples crystallize with the spinel crystal structure (S.G. Fd3-m). The cubic unit-cell parameter increases with the Ti content. The influence of the Ti content and cationic distribution on the magnetic properties of the compounds was studied by measuring the temperature and magnetic field dependences of the magnetization: substitution by non-magnetic d0 Ti4+ ions appeared to weaken the magnetic interactions between the manganese ions. The electrical properties of LiMnTiO4 were studied by AC impedance spectroscopy and DC polarisation measurements, which revealed the electronic character of the conduction process. © 2006 Elsevier B.V. All rights reserved.

Anisotropic behaviour in the magnetic field dependence of the low temperature electrical resistance of calcium-doped lanthanum manganate thin films grown by RF magnetron sputtering

We report about the magnetoresistive properties of calcium-doped lanthanum manganate thin films grown by RF magnetron sputtering on single crystalline LaAlO3 and MgO substrates. Two orientations of the magnetic field with respect to the electrical current have been studied: (i) magnetic field in the plane of the film and parallel to the electrical current, and (ii) magnetic field perpendicular to the plane of the film. The film grown on LaAlO 3 is characterised by an unusual magnetoresistive behaviour when the magnetic field is applied perpendicular to the film plane: the appearance of two bumps in the field dependence of the resistance is shown to be related to the occurrence of anisotropic magnetoresistive effects in manganate films. © 2004 Elsevier B.V. All rights reserved.

Effects of silicon addition on the electrical and magnetic properties of copper-doped (La,Ca)MnO3 compounds

In this paper we report about the electrical properties of La 0.7Ca0.3MnO3 compounds substituted by copper on the manganese site and/or deliberately contaminated by SiO2 in the reactant mixture. Several phenomena have been observed and discussed. SiO2 addition leads to the formation of an apatite-like secondary phase that affects the electrical conduction through the percolation of the charge carriers. On the other hand, depending on the relative amounts of copper and silicon, the temperature dependence of the electrical resistivity can be noticeably modified: our results enable us to compare the effects of crystallographic vacancies on the A and B sites of the perovskite with the influence of the copper ions substituted on the manganese site. The most original result occurs for the compounds with a small ratio Si/Cu, which display double-peaked resistivity vs. temperature curves. © 2003 Elsevier B.V. All rights reserved.