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.

Electrochemical H2S sensor with H2SO4 pre-treated Nafion membrane as solid polymer electrolyte

It is reported for the first time that the performance of the electrochemical H2S sensor with the Nation membrane pre-treated with the concentrated H2SO4 as the solid electrolyte is much more stable than that for the sensor with the Nation membrane without H2SO4 pretreatment. The sensitivity of the sensor is about 2.92 muA/ppm. The response time of the sensor is about 9 s. The detection limit is about 0.1 ppm. Therefore, this kind of the electrochemical H2S gas sensor may be desirable for the practical application.

COLORIMETRIC POLYMER FILM SENSORS FOR DISSOLVED CARBON-DIOXIDE

Plasticized and unplasticized polymer colorimetric film sensors for gaseous CO2, containing the dye m-cresol purple, are tested as sensors for dissolved CO2. The plasticized polymer m-cresol purple film sensor develops a measurable degree of opacity when exposed to aqueous solution, especially in neutral, compared with alkaline, solution. However, it is shown that a presoaked, fogged plasticized polymer m-cresol purple film does function as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. An unplasticized polymer m-cresol purple film remains largely dear upon exposure to aqueous solution and also functions as a quantitative sensor for dissolved CO2 over the range 0-4% CO2. However, in both types of films the dye interacts with electrolytes present in solution; invariably the dye appears to be converted from its initial deprotonated form (blue) to its protonated form (yellow) and the rate of this process appears to increase with increasing ionic strength, anionic charge and decreasing pH. The 90% response and recovery times for an unplasticized film are determined as 19 s(CO2:0-->5%) and 21 s (CO2:5-->3.6%), respectively.

A selective conductive polymer-based sensor for volatile halogenated organic compounds (VHOC)

A novel poly(p-xylylene), PPX, derivative bearing alkoxyphenyl side groups was electrochemically synthesized in 87% yield. The polymer, poly(4`-hexyloxy-2,5-biphenyleneethylene) (PHBPE), presented a fraction (92%) soluble in common organic solvents. It showed to be thermally resistant up to 185 degrees C. UV-vis analysis revealed an E-gap of 3.5 eV Gas sensors made from thin films of 10-camphorsulfonic acid-doped PHBPE deposited on interdigitated electrodes exhibited significant changes in electrical conductance upon exposure to five VHOCs: 1,2-dichloroethane, bromochloromethane, trichloromethane, dichloromethane and tetrachloromethane. The conductance decreased after exposure to tetrachloromethane and increased after exposure to all the other VHOCs. Three-dimensional plots of relative response versus time of half response versus time of half recovery showed good discrimination between the five VHOCs tested. (c) 2008 Elsevier B.V. All rights reserved.

Synthesis, characterization and analytical modelling of mechanical behavior of a conducting polymer actuator

Electrochemical synthesis of a tri-layer polypyrrole based actuator optimized for performance was reported. The 0.05 M pyrrole and 0.05 M tetrabutylammonium hexaflurophosphate in propylene carbonate (PC) yielded the optimum performance and stability. The force produced ranged from 0.2 to 0.4mN. Cyclic deflection tests on PC based actuators for 3 hours indicated that the displacement decreased by 60%. PC based actuator had a longer operating time, exceeding 3 hours, compared to acetonitrile based actuators. A triple-layer model of the polymer actuator was developed based on the classic bending beam theory by considering strain electrode material. A tri-layer actuator was fabricated [4, 6], by initially sputter coating a PVDF film with approximately 100nm of gold layer, resulting in a conductive film with a surface resistance of 8-10Ω. The PVDF film was about ~145µm thick had an approximate pore size of 45μm. A solution containing 0.05M distilled pyrrole monomer, 0.05M (TBAPF6) and 1% (w/w) distilled water in PC (propylene carbonate) solution was purged with nitrogen for 15 minutes. The continuity between PPy and PVDF. Results predicted by the model were in good agreement with the experimental data.

Use of ionic liquids for π-conjugated polymer electrochemical devices

π-Conjugated polymers that are electrochemically cycled in ionic liquids have enhanced lifetimes without failure (up to 1 million cycles) and fast cycle switching speeds (100 ms). We report results for electrochemical mechanical actuators, electrochromic windows, and numeric displays made from three types of π-conjugated polymers: polyaniline, polypyrrole, and polythiophene. Experiments were performed under ambient conditions, yet the polymers showed negligible loss in electroactivity. These performance advantages were obtained by using environmentally stable, room-temperature ionic liquids composed of 1-butyl-3-methyl imidazolium cations together with anions such as tetrafluoroborate or hexafluorophosphate.

Mass/charge balance as a tool to estimate dimensional change in polypyrrole-based actuators

The deconvolution of the voltammograms of polypyrrole electrochemistry has proved to be possible through the electrochemical quartz crystal microbalance data using the F(dm/dQ) function. This deconvolution allows the evolution of the thickness of the polypyrrole films during their redox processes to be estimated and therefore, the mechanical contraction/decontraction of this polymer as a function of the ionic exchange processes can be evaluated. (c) 2005 Elsevier B.V. All rights reserved.

Development of microvalves for gas flow control in micronozzles using PVDF piezoelectric polymer

This work describes a fabrication and test sequence of microvalves installed on micronozzles. The technique used to fabricate the micronozzles was powder blasting. The microvalves are actuators made from PVDF (polivinylidene fluoride), that is a piezoelectric polymer. The micronozzles have convergent-divergent shape with external diameter of 1mm and throat around 230μm. The polymer have low piezoelectric coefficient, for this reason a bimorph structure with dimensions of 2mm width and 4mm of length was build (two piezoelectric sheets were glued together with opposite polarization). Both sheets are recovered with a conductor thin film used as electrodes. Applying a voltage between the electrodes one sheet expands while the other contracts and this generate a vertical movement to the entire actuator. Appling +300V DC between the electrodes the volume flux rate, for a pressure ratio of 0.5, was 0.36 sccm. Applying -200V DC between the electrodes (that means it closed) the volume flux rate was 0.32 sccm, defining a possible range of flow between 0.32 and 0.36 sccm. The third measurement was performed using AC voltage (200V AC with frequency of 1Hz), where the actuator was oscillating. For pressure ratio of 0.5, the flow rate was 0.62 sccm. © 2008 IOP Publishing Ltd.

Surface patterned polymer micro-cantilever arrays for sensing

Microinjection molding was employed to fabricate low-cost polymer cantilever arrays for sensor applications. Cantilevers with micrometer dimensions and aspect ratios as large as 10 were successfully manufactured from polymers, including polypropylene and polyvinylidenfluoride. The cantilevers perform similar to the established silicon cantilevers, with Q-factors in the range of 10–20. Static deflection of gold coated polymer cantilevers was characterized with heat cycling and self-assembled monolayer formation of mercaptohexanols. A hybrid mold concept allows easy modification of the surface topography, enabling customized mechanical properties of individual cantilevers. Combined with functionalization and surface patterning, the cantilever arrays are qualified for biomedical applications

Organic distributed feedback laser to monitor solvent extraction upon thermal annealing in solution-processed polymer films

Solution-processed polymer films are used in multiple technological applications. The presence of residual solvent in the film, as a consequence of the preparation method, affects the material properties, so films are typically subjected to post-deposition thermal annealing treatments aiming at its elimination. Monitoring the amount of solvent eliminated as a function of the annealing parameters is important to design a proper treatment to ensure complete solvent elimination, crucial to obtain reproducible and stable material properties and therefore, device performance. Here we demonstrate, for the first time to our knowledge, the use of an organic distributed feedback (DFB) laser to monitor with high precision the amount of solvent extracted from a spin-coated polymer film as a function of the thermal annealing time. The polymer film of interest, polystyrene in the present work, is doped with a small amount of a laser dye as to constitute the active layer of the laser device and deposited over a reusable DFB resonator. It is shown that solvent elimination translates into shifts in the DFB laser wavelength, as a consequence of changes in film thickness and refractive index. The proposed method is expected to be applicable to other types of annealing treatments, polymer-solvent combinations or film deposition methods, thus constituting a valuable tool to accurately control the quality and reproducibility of solution-processed polymer thin films.

The performance of poly(styrene)-block-poly(2-vinyl pyridine)-block- poly(styrene) triblock copolymers as pH-driven actuators

Poly(styrene)-block-poly(2-vinyl pyridine)-block-poly(styrene) (PS-b-P2VP-b-PS) triblock copolymers were synthesised by anionic polymerisation. Thick films were cast from solution and their structure analysed by small angle X-ray scattering (SAXS). Longer annealing times led to more ordered structures whereas short evaporation times effectively "lock" the polymer chains in a disordered state by vitrification. Well-ordered structures not only provide an isotropic network, which reduces localised stress within the material, but are also essential for fundamental studies of soft matter because their activity on the molecular scale must be analysed and understood prior to their use in technological applications. Well-characterised PS-b-P2VP-b-PS materials have been coupled to a pH-oscillating reaction and their potential application as responsive actuators is discussed. This journal is © The Royal Society of Chemistry.

A fast response intrinsic humidity sensor based on an etched singlemode polymer fiber Bragg grating

A simple, low cost and fast response time intrinsic relative humidity sensor system based on an etched singlemode polymer fiber Bragg (POFBG) is presented in this paper. A macro-bend linear edge filter which converts the humidity induced wavelength shift into an intensity change is used as the interrogation technique. The singlemode POFBG is etched to micro-meters in diameter to improve the response time of the humidity sensor. A response time of 4.5 s is observed for a polymer FBG with a cladding diameter of 25 μm. The overall sensor system sensitivity was 0.23 mV/%RH. The etched POFBG humidity sensor shows anexponential decrease in response time with a decrease in fiber diameter. The developed sensor might have potential applications in a wide range of applications where fast and accurate real time humidity control is required. © 2013 Elsevier B.V. All rights reserved.