Use of the Optical Cantilever Microphone in Photoacoustic Spectroscopy

A novel cantilever pressure sensor was developed in the Department of Physics at the University of Turku in order to solve the sensitivity problems which are encountered when condenser microphones are used in photoacoustic spectroscopy. The cantilever pressure sensor, combined with a laser interferometer for the measurement of the cantilever movements, proved to be highly sensitive. The original aim of this work was to integrate the sensor in a photoacoustic gas detector working in a differential measurement scheme. The integration was made successfully into three prototypes. In addition, the cantilever was also integrated in the photoacoustic FTIR measurement schemes of gas-, liquid-, and solid-phase samples. A theoretical model for the signal generation in each measurement scheme was created and the optimal celldesign discussed. The sensitivity and selectivity of the differential method were evaluated when a blackbody radiator and a mechanical chopper were used with CO₂, CH4, CO, and C2H4 gases. The detection limits were in the sub-ppm level for all four gases with only a 1.3 second integration time and the cross interference was well below one percent for all gas combinations other than those between hydrocarbons. Sensitivity with other infrared sources was compared using ethylene as an example gas. In the comparison of sensitivity with different infrared sources the electrically modulated blackbody radiator gave a 35 times higher and the CO2-laser a 100 times lower detection limit than the blackbody radiator with a mechanical chopper. As a conclusion, the differential system is well suited to rapid single gas measurements. Gas-phase photoacoustic FTIR spectroscopy gives the best performance, when several components have to be analyzed simultaneously from multicomponent samples. Multicomponent measurements were demonstrated with a sample that contained different concentrations of CO₂, H₂O, CO, and four different hydrocarbons. It required an approximately 10 times longer measurement time to achieve the same detection limit for a single gas as with the differential system. The properties of the photoacoustic FTIR spectroscopy were also compared to conventional transmission FTIR spectroscopy by simulations. Solid- and liquid-phase photoacoustic FTIR spectroscopy has several advantages compared to other techniques and therefore it also has a great variety of applications. A comparison of the signal-to-noise ratio between photoacoustic cells with a cantilever microphone and a condenser microphone was done with standard carbon black, polyethene, and sunflower oil samples. The cell with the cantilever microphone proved to have a 5-10 times higher signal-to-noise ratio than the reference detector, depending on the sample. Cantilever enhanced photoacoustics will be an effective tool for gas detection and analysis of solid- and liquid-phase samples. The preliminary prototypes gave good results in all three measurement schemes that were studied. According to simulations, there are possibilities for further enhancement of the sensitivity, as well as other properties, of each system.

Three Wavelength Optical Probe for Surface Roughness Measurements of Paper Samples

In the present diploma work optical inspection methods were used to investigate surface roughness of paper samples. A special measurement setup, which includes three laser light sources of three different wavelengths, photodetector and goniometer, was used to measure the reflected laser light properties. The intensity of the light reflected in specular direction was measured versus the laser incidence angle for reference metal sample. The value of roughness was estimated and compared to initially known value of metal sample roughness. Thus, the measurement equipment and method were validated. Then the reflected intensity was measured versus reflection angle at constant incidence angle for the same metal sample and paper samples under investigation. The final values of the surface roughness were obtained from the analysis of the reflected intensity dependence. The results are in good correlation with other research groups.

Surface passivation and optical characterization of Al2O3/a-SiCx stacks on c-Si substrates

Postprint (published version)

All-Optical Unicast/Multicast Routing in WDM Networks

Optical transport networks (OTN) must be prepared in terms of better resource utilization, for accommodating unicast and multicast traffic together. Light-trees have been proposed for supporting multicast connections in OTN. Nevertheless when traffic grooming is applied in light-trees, resources can be underutilized as traffic can be routed to undesirable destinations in order to avoid optical-electrical-optical (OEO) conversions. In this paper, a novel architecture named S/G light- tree for supporting unicast/multicast connections is proposed. The architecture allows traffic dropping and aggregation in different wavelengths without performing OEO conversions. A heuristic that routes traffic demands using less wavelengths by taking advantage of the proposed architecture is designed as well. Simulation results show that the architecture can minimize the number of used wavelengths and OEO conversions when compared to light-trees

Polychlorinated dibenzo-p-dioxins (PCDD), dibenzofurans (PCDF) and polychlorinated biphenyls (PCB): main sources, environmental behaviour and risk to man and biota

Polychlorinated dibenzo-p-dioxins (PCDD) and dibenzofuranes (PCDF) and polychlorinated biphenyls (PCB) are types of persistent and bioaccumulating organic pollutants with enhanced chronic toxicity and carcinogenic properties and can be considered as environmental indicators of anthropogenic activities since their occurrence in the environment can always be linked to anthropogenic activities. The present paper reviews the main sources and behaviour of these compounds in the environment as well as the risks they represent to man and biota.

Aerossóis atmosféricos: perspectiva histórica, fontes, processos químicos de formação e composição orgânica

This work starts with a historical perspective of the social and scientific progress related to the understanding of the atmospheric aerosol. Its origin, physical, chemical and optical characteristics, as well as its environmental behaviour are described, retracing the evolution of the concepts related to this subject over the last centuries. The main sources that contribute to atmospheric particulate matter and the modern understanding of its formation processes and constitution, focusing on the chemical pathways leading to it and on its organic components are presented. This discussion is complemented with recent evaluations of the quantities emitted by primary, secondary, biogenic and anthropogenic sources and the effects due to accumulation or dispersion of aerosols, justifying the chemical and environmental interest they engender.

Uso de membranas de Nafion para a construção de sensores ópticos para medidas de pH

The behaviour of Nafion® polymeric membranes containing acid-base dyes, bromothymol blue (BB) and methyl violet (MV), were studied aiming at constructing an optical sensor for pH measurement. BB revealed to be inadequate for developing sensing phases due to the electrostatic repulsion between negative groups of their molecules and the negative charge of the sulfonate group of the Nafion®, which causes leaching of the dye from the membrane. On the other hand, MV showed to be suitable due to the presence of positive groups in its structure. The membrane prepared from a methanolic solution whose Nafion®/dye molar ratio was 20 presented the best analytical properties, changing its color from green to violet in the pH range from 0.6 to 3.0. The membrane can be prepared with good reproducibility, presenting durability of ca. 6 months and response time of 22 s, making possible its use for pH determination in flow analysis systems.

A novel method for fast enrichment and monitoring of hexavalent and trivalent chromium at the ppt level with modified silica MCM-41 and its determination by inductively coupled plasma optical emission spectrometry

Chromium(III) at the ng L-1 level was extracted using partially silylated MCM-41 modified by a tetraazamacrocyclic compound (TAMC) and determined by inductively coupled plasma optical emision spectrometry (ICP OES). The extraction time and efficiency, pH and flow rate, type and minimum amount of stripping acid, and break- through volume were investigated. The method's enrichment factor and detection limit are 300 and 45.5 pg mL-1, respectively. The maximum capacity of the 10 mg of modified silylated MCM-41 was found to be 400.5±4.7 µg for Cr(III). The method was applied to the determination of Cr(III) and Cr(VI) in the wastewater of the chromium electroplating industry and in environmental and biological samples (black tea, hot and black pepper).

Synthesis, characterization and thermal behaviour of solid-state compounds of benzoates with some bivalent transition metal ions

Solid-state MBz compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu and Zn and Bz is benzoate, have been synthesized. Simultaneous thermogravimetry and differential thermal analysis (TG-DTA), differential scanning calorimetry (DSC), infrared spectroscopy and complexometry were used to characterize and to study the thermal behaviour of these compounds. The procedure used in the preparation of the compounds via reaction of basic carbonates with benzoic acid is not efficient in eliminating excess acid. However the TG-DTA curves permitted to verify that the binary compounds can be obtained by thermosynthesis, because the benzoic acid can be eliminated before the thermal decomposition of these compounds. The results led to information about the composition, dehydration, thermal stability, thermal decomposition and structure of the isolated compounds. On heating, these compounds decompose in two (Mn, Co, Ni, Zn) or three (Fe, Cu) steps with formation of the respective oxide (Mn3O4, Fe2O3, Co3O4, NiO, CuO and ZnO) as final residue. The theoretical and experimental spectroscopic studies suggest a covalent bidentate bond between ligand and metallic center.

Optical and microstructural properties of MgF2 UV coatings grown by ion beam sputtering process

The optical, mechanical, and microstructural properties of MgF2 single layers grown by ion beam sputtering have been investigated by spectrophotometric measurements, film stress characterization, x-ray photoelectron spectroscopy (XPS), x-ray diffraction, and transmission electron microscopy. The deposition conditions, using fluorine reactive gas or not, have been found to greatly influence the optical absorption and the stress of the films as well as their microstructure. The layers grown with fluorine compensation exhibit a regular columnar microstructure and an UV-optical absorption which can be very low, either as deposited or after thermal annealings at very low temperatures. On the contrary, layers grown without fluorine compensation exhibit a less regular microstructure and a high ultraviolet absorption which is particularly hard to cure. On the basis of calculations, it is shown that F centers are responsible for this absorption, whereas all the films were found to be stoichiometric, in the limit of the XPS sensitivity. On the basis of external data taken from literature, our experimental curves are analyzed, so we propose possible diffusion mechanisms which could explain the behaviors of the coatings.

Alternative technique for biodiesel quality control using an optical fiber long-period grating sensor

We report the use of an optical fiber sensor to measure the soybean oil concentration in samples obtained from the mixture of pure biodiesel and commercial soybean oil. The operation of the device is based on the long-period grating sensitivity to the surrounding medium refractive index, which leads to measurable modifications in the grating transmission spectrum. The proposed analysis method results in errors in the oil concentration of 0.4% and 2.6% for pure biodiesel and commercial soybean oil, respectively. Techniques of total glycerol, dynamic viscosity, density, and hydrogen nuclear magnetic resonance spectroscopy were also employed to validate the proposed method.

Relationships between adolescents and parents values and parents answering behaviour

In this paper we set out a confirmatory factor analysis model relating the values adolescents and their parents aspire to for the child’s future. We approach a problem when collecting parents’ answers and analysing paired data from parents and their child: the fact that in some families only one parent answers, while in others both meet to answer together. In order to account for differences between one-parent and two-parent responses we follow a multiple group structural equation modelling approach. Some significant differences emerged between the two and one answering parent groups. We observed only weak relationships between parents’ and children’s values

Preparation of glasses and glass ceramics of heavy metal oxides containing silver: optical, structural and electrochemical properties

Silver containing heavy metal oxide glasses and glass ceramics of the system WO3-SbPO4-PbO-AgCl with different AgCl contents have been prepared and their thermal, structural and optical properties characterized. Glass ceramics containing metallic silver nanoparticles have been prepared by annealing glass samples at temperatures above the glass transition and analyzed by transmission electron microscopy and energy dispersive X-ray microanalysis. The presence of the metallic clusters has been also confirmed by the observation of a surface plasmon resonance band in the visible range. Cyclic voltammetric measurements indicated the presence of metallic silver into the glasses, even before to perform the thermal treatment.

Development of an optical redox chemical sensor for nitrite determination

An optical chemical sensor for the determination of nitrite based on incorporating methyltrioctylammonium chloride as an anionic exchanger on the triacetylcellulose polymer has been reported. The response of the sensor is based on the redox reaction between nitrite in aqueous solution and iodide adsorbed on sensing membrane using anion exchange phenomena. The sensing membrane reversibly responses to nitrite ion over the range of 6.52×10-6 - 8.70×10-5 mol L-1 with a detection limit of 6.05×10-7 mol L-1 (0.03 µg mL-1) and response time of 6 min. The relative standard deviation for eight replicate measurements of 8.70×10-6 and 4.34×10-5 mol L-1 of nitrite was 4.4 and 2.5 %, respectively. The sensor was successfully applied for determination of nitrite in food, saliva and water samples.