Agnieszka Stolarczyk

Studies of Reduced Graphene Oxide and Graphite Oxide in the Aspect of Their Possible Application in Gas Sensors

The paper presents the results of investigations on resistance structures based on graphite oxide (GRO) and graphene oxide (rGO). The subject matter of the investigations was thaw the sensitivity of the tested structures was affected by hydrogen, nitrogen dioxide and carbon dioxide. The experiments were performed at a temperature range from 30 °C to 150 °C in two carrier gases: nitrogen and synthetic air. The measurements were also aimed at characterization of the graphite oxide and graphene oxide. In our measurements we used (among others) techniques such as: Atomic Force Microscopy (AFM); Scanning Electron Microscopy (SEM); Raman Spectroscopy (RS); Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Microscopy (XPS). The data resulting from the characterizations of graphite oxide and graphene oxide have made it possible to interpret the obtained results from the point of view of physicochemical changes occurring in these structures.

A Study of a QCM Sensor Based on TiO2 Nanostructures for the Detection of NO2 and Explosives Vapours in Air

The paper deals with investigations concerning the construction of sensors based on a quartz crystal microbalance (QCM) containing a TiO2 nanostructures sensor layer. A chemical method of synthesizing these nanostructures is presented. The prepared prototype of the QCM sensing system, as well as the results of tests for detecting low NO2 concentrations in an atmosphere of synthetic air have been described. The constructed NO2 sensors operate at room temperature, which is a great advantage, because resistance sensors based on wide gap semiconductors often require much higher operation temperatures, sometimes as high as 500 °C. The sensors constructed by the authors can be used, among other applications, in medical and chemical diagnostics, and also for the purpose of detecting explosive vapours. Reactions of the sensor to nitroglycerine vapours are presented as an example of its application. The influence of humidity on the operation of the sensor was studied.

Influence of External Gaseous Environments on the Electrical Properties of ZnO Nanostructures Obtained by a Hydrothermal Method

This paper deals with experimental investigations of ZnO nanostructures, consisting of a mixture of nanoparticles and nanowires, obtained by the chemical (hydrothermal) method. The influences of both oxidizing (NO2) and reducing gases (H2, NH3), as well as relative humidity (RH) on the physical and chemical properties of ZnO nanostructures were tested. Carrier gas effect on the structure interaction with gases was also tested; experiments were conducted in air and nitrogen (N2) atmospheres. The effect of investigated gases on the resistance of the ZnO nanostructures was tested over a wide range of concentrations at room temperature (RT) and at 200 °C. The impact of near- ultraviolet (UV) excitation (λ = 390 nm) at RT was also studied. These investigations indicated a high response of ZnO nanostructures to small concentrations of NO2. The structure responses to 1 ppm of NO2 amounted to about: 600% in N2/230% in air at 200 °C (in dark conditions) and 430% in N2/340% in air at RT (with UV excitation). The response of the structure to the effect of NO2 at 200 °C is more than 105 times greater than the response to NH3, and more than 106 times greater than that to H2 in the relation of 1 ppm. Thus the selectivity of the structure for NO2 is very good. What is more, the selectivity to NO2 at RT with UV excitation increases in comparison at elevated temperature. This paper presents a great potential for practical applications of ZnO nanostructures (including nanoparticles) in resistive NO2 sensors.

A Study on the Impact of Poly(3-hexylthiophene) Chain Length and Other Applied Side-Chains on the NO2 Sensing Properties of Conducting Graft Copolymers

The detection and concentration measurements of low concentrations of nitrogen dioxide (NO2) are important because of its negative effects on human health and its application in many fields of industry and safety systems. In our approach, conducting graft copolymers based on the poly(3-hexylthiophene) (P3HT) conducting polymer and other side-chains, polyethylene glycol (PEG) and dodec-1-en, grafted on a poly(methylhydrosiloxane) backbone, were investigated. The grafts containing PEG (PEGSil) and dodec-1-en (DodecSil) in two variants, namely, fractions with shorter (hexane fraction -H) and longer (chloroform fraction -CH) side-chains of P3HT, were tested as receptor structures in NO2 gas sensors. Their responses to NO2, within the concentration range of 1–20 ppm, were investigated in an nitrogen atmosphere at different operating temperatures—room temperature (RT) = 25 °C, 50 °C, and 100 °C. The results indicated that both of the copolymers with PEG side-chains had higher responses to NO2 than the materials with dodec-1-en side-chains. Furthermore, the results indicated that, in both cases, H fractions were more sensitive than CH fractions. The highest response to 1 ppm of NO2, from the investigated graft copolymers, had PEGSil H, which indicated a response of 1330% at RT and 1980% at 100 °C. The calculated lower-limit of the detection of this material is lower than 300 ppb of NO2 at 100 °C. This research indicated that graft copolymers of P3HT had great potential for low temperature NO2 sensing, and that the proper choice of other side-chains in graft copolymers can improve their gas sensing properties.

A low temperature operated NO2 gas POF sensor based on conducting graft polymer

The paper presents the way that colour can serve solving the problem of calibration points indexing in a camera geometrical calibration process. We propose a technique in which indexes of calibration points in a black-and-white chessboard are represented as sets of colour regions in the neighbourhood of calibration points. We provide some general rules for designing a colour calibration chessboard and provide a method of calibration image analysis. We show that this approach leads to obtaining better results than in the case of widely used methods employing information about already indexed points to compute indexes. We also report constraints concerning the technique. Nowadays we are witnessing an increasing need for camera geometrical calibration systems. They are vital for such applications as 3D modelling, 3D reconstruction, assembly control systems, etc. Wherever possible, calibration objects placed in the scene are used in a camera geometrical calibration process. This approach significantly increases accuracy of calibration results and makes the calibration data extraction process easier and universal. There are many geometrical camera calibration techniques for a known calibration scene [1]. A great number of them use as an input calibration points which are localised and indexed in the scene. In this paper we propose the technique of calibration points indexing which uses a colour chessboard. The presented technique was developed by solving problems we encountered during experiments with our earlier methods of camera calibration scene analysis [2]-[3]. In particular, the proposed technique increases the number of indexed points points in case of local lack of calibration points detection. At the beginning of the paper we present a way of designing a chessboard pattern. Then we describe a calibration point indexing method, and finally we show experimental results. A black-and-white chessboard is widely used in order to obtain sub-pixel accuracy of calibration points localisation [1]. Calibration points are defined as corners of chessboard squares. Assuming the availability of rough localisation of these points, the points can be indexed. Noting that differences in distances between neighbouring points in calibration scene images differ slightly, one of the local searching methods can be employed (e.g. [2]). Methods of this type search for a calibration point to be indexed, using a window of a certain size. The position of the window is determined by a vector representing the distance between two previously indexed points in the same row or column. However, experiments show that this approach has its disadvantages, as described below. * E-mail: A.Nowakowski@ire.pw.edu.pl Firstly, there is a danger of omitting some points during indexing in case of local lack of calibration points detection in a neighbourhood (e.g. caused by the presence of non-homogeneous light in the calibration scene). A particularly unfavourable situation is when the local lack of detection effects in the appearance of separated regions of detected calibration points. It is worth saying that such situations are likely to happen for calibration points situated near image borders. Such points are very important for the analysis of optical nonlinearities, and a lack of them can significantly influence the accuracy of distortion modelling. Secondly, such methods may give wrong results in the case of optical distortion with strong nonlinearities when getting information about the neighbouring index is not an easy task. Beside this, the methods are very sensitive to a single false localisation of a calibration point. Such a single false localisation can even result in false indexing of a big set of calibration points. To avoid the above-mentioned problems, we propose using a black-and-white chessboard which contains the coded index of a calibration point in the form of colour squares situated in the nearest neighbourhood of each point. The index of a certain calibration point is determined by colours of four nearest neighbouring squares (Fig.1). An order of squares in such foursome is important. Because the size of a colour square is determined only by the possibility of correct colour detection, the size of a colour square can be smaller than the size of a black or white square. The larger size of a black or white square is determined by the requirements of the exact localisation step which follows the indexing of calibration points [3]. In this step, edge information is extracted from a blackand-white chessboard. This edge information needs larger Artur Nowakowski, Wladyslaw Skarbek Institute of Radioelectronics, Warsaw University of Technology, Nowowiejska 15/19, 00-665 Warszawa, A.Nowakowski@ire.pw.edu.pl Received February 10, 2009; accepted March 27, 2009; published March 31, 2009 http://www.photonics.pl/PLP

Impact of Temperature and UV Irradiation on Dynamics of NO2 Sensors Based on ZnO Nanostructures

The main object of this study is the improvement of the dynamics of NO2 sensors based on ZnO nanostructures. Investigations presented in this paper showed that the combination of temperature and ultraviolet (UV) activation of the sensors can significantly decrease the sensor response and regeneration times. In comparison with the single activation method (elevated temperature or UV), these times for 1 ppm of NO2 decreased from about 10 min (or more) to less than 40 s. In addition, at the optimal conditions (200 °C and UV), sensors were very stable, were fully scalable (in the range on NO2 concentration of 1–20 ppm) and baseline drift was significantly reduced. Furthermore, in this paper, extensive studies of the influence of temperature and carrier gas (nitrogen and air) on NO2 sensing properties of the ZnO nanostructures were conducted. The NO2 sensing mechanisms of the sensors operating at elevated temperatures and under UV irradiation were also discussed. Our study showed that sensor responses to NO2 and response/regeneration times are comparable from sensor to sensor in air and nitrogen conditions, which suggests that the proposed simple technology connected with well-chosen operation conditions is repeatable. The estimated limit of detection of the sensors is within the level of ≈800 ppb in nitrogen and ≈700 ppb in air.

Surface plasmon resonance study of comb copolymers containing regioregular poly-3-hexylothiophene

The surface plasmon resonance (SPR) is very sensitive, and so is the optical technique used in chemical sensing. The angle of incident of light at which a resonant effect is observed, as well as the dip of a resonant are very sensitive to variations of the optical parameters of the medium on a surface-active plasmon metal layer. In this work a novel combcopolimer of regioregular poly-3-hexylothiophene (rr-P3HT) and is studied as a gas (NO2) sensing material. Gas sensing properties of this material is examined using SPR technique at room temperature.

Spectroelectrochemistry of poly(3-hexylthiophenes) in solution

The first comprehensive spectroelectrochemical account of the behaviour of regioregular (RR-P3HT) and statistical (ST-P3HT) poly(3-hexylthiophenes) in solution is presented, in contrast to the many reports dealing with P3HT films merely deposited from solution. The conducted experiments revealed that the two types of P3HTs behave in sharply different ways upon the application of electrochemical stimuli: ST-P3HT readily precipitates at mildly oxidative potentials, while the precipitation of the RR-P3HT takes place to a much lesser extent, even at higher potentials. The two polymers, studied via UV–Vis–NIR–EPR spectroelectrochemistry, exhibited properties mostly in line with earlier reports. Further study revealed that RR-P3HT largely remains in solution, even in its doped form, whereas only traces of the doped ST-P3HT are observed in solution in identical conditions. The high concentration of the doped RR-P3HT in solution can be explained by its ability to form soluble polymer agglomerates, in which the positive charge of the p-doped chains is stabilised by and delocalised over neighbouring, interacting undoped chains. These conclusions are consistent with SEM micrographs, which show that after cycling the potential of the electrode in a solution of ST-P3HT, a uniform layer is formed, covering most of the surface of the electrode, whereas in the case of RR-P3HT surface coverage is marginal and formed layer has the appearance of veined blotches.Graphical abstract

The influence of oxygen conditioning effect on the permeation properties of polyaniline membranes

ABSTRACT The effect of oxygen conditioning on the performance of polyaniline (PANI) membranes is presented and discussed. The presence of the conditioning effect in such kind of polymer matrix was confirmed by measuring a variation in spin concentration using electron paramagnetic resonance (EPR) spectroscopy. The observed decrease in spin concentration indicates the presence of the dissolved oxygen incompletely removed from PANI matrix. After the prolonged contact between oxygen and PANI membrane, a pronounced decrease in membrane’s selectivity was observed, which may be explained by the firm and permanent interaction between oxygen molecules and nitrogen paramagnetic centers of PANI and could be considered as a kind of PANI irreversible doping process.

Atomic and electronic structure of graphene oxide/Cu interface

Abstract The results of X-ray photoemission (XPS) and valence bands spectroscopy, optically stimulated electron emission (OSEE) measurements and density functional theory based modeling of graphene oxide (GO) placed on Cu via an electrophoretic deposition (EPD) are reported. The comparison of XPS spectra of EPD prepared GO/Cu composites with those of as prepared GO, strongly reduced GO, pure and oxidized copper demonstrate the partial (until C/O ratio about two) removal of oxygen-containing functional groups from GO simultaneously with the formation of copper oxide-like layers over the metallic substrate. OSEE measurements evidence the presence of copper oxide phase in the systems simultaneously with the absence of contributions from GO with corresponding energy gap. All measurements demonstrate the similarity of the results for different thickness of GO cover of the copper surface. Theoretical modeling demonstrates favorability of migration of oxygen-containing functional groups from GO to the copper substrate only for the case of C/O ratio below two and formation of Cu-O-C bonds between substrate and GO simultaneously with the vanishing of the energy gap in GO layer. Basing on results of experimental measurements and theoretical calculations we suggest the model of atomic structure for Cu/GO interface as Cu/CuO/GO with C/O ratio in gapless GO about two.