Kinetic measurements during transient film growth on zinc

The electrochemical behaviour of zinc has been extensively studied in alkaline and acid media, but only a few studies have been reported in neutral solutions, particularly in deaerated media. Zinc passivation in neutral medium and the effect of the ClO4- ion on the nucleation and growth of the passive layer is studied in this paper by a transient technique at different electrolyte concentrations and applied potentials. ZnO growth rate was shown to decrease with increasing electrolyte concentration. Moreover, passive layer growth occurred followed by pitting nucleation and growth. Film growth and pit nucleation are explained by means of the Macdonald and Engell-Stolica models.

Temperature measurements by oh lif and chemiluminescence kinetic modeling for ethanol flames

OH LIF-thermometry was applied to premixed ethanol flames at atmospheric pressure in a burner for three flame conditions. Flame temperatures were simulated from energy equation with PREMIX code of CHEMKIN software package for comparison. A kinetic modeling based on a model validated through chemiluminescence measurements and on a set of reactions for nitrogen chemistry was evaluated. Marinov's mechanism was also tested. Sensitivity analysis was performed for fuel-rich flame condition with Φ = 1.34. Simulated temperatures from both reaction mechanisms evaluated were higher than experimental values. However, the proposed kinetic modeling resulted in temperature profiles qualitatively very close to the experimental.

Structural and reactivity analyses of 2-benzylamino-1,4-naphthoquinone by X-ray characterization, electrochemical measurements, and dft single-molecule calculations

This study represents an integrated approach towards understanding the electronic and structural aspects of 2-benzylamino-1,4-naphthalenedione, a representative 2-amino-napfthoquinone. To this end, theoretical calculations performed at the B3PW91/6-31+G(d) level of density functional theory, electrochemical and X-ray structural investigation were employed. Two intramolecular H-bonds and other two intermolecular H-bonds were observed, including non-classical interactions. Cyclic voltammogram (CV) and differential pulse voltammetry (DPV) show two pairs of peaks, being each one a monoelectronic process.

Organic and total mercury determination in sediments by cold vapor atomic absorption spectrometry: methodology validation and uncertainty measurements

The purpose of the present study was to validate a method for organic Hg determination in sediment. The procedure for organic Hg was adapted from literature, where the organomercurial compounds were extracted with dichloromethane in acid medium and subsequent destruction of organic compounds by bromine chloride. Total Hg was performed according to 3051A USEPA methodology. Mercury quantification for both methodologies was then performed by CVAAS. Methodology validation was verified by analyzing certified reference materials for total Hg and methylmercury. The uncertainties for both methodologies were calculated. The quantification limit of 3.3 µg kg-1 was found for organic Hg by CVAAS.

Screening of sweet sorghum accessions for inhibition of secondary sporulation and saccharide measurements in honeydew of Claviceps africana

Certain sweet sorghums (Sorghum bicolor) inhibit the secondary sporulation of Claviceps africana, which occurs on exuded ergot honeydew when the parasite is supplied with excess sucrose, which is then transformed to unique free oligosaccharides fructosyl - mannitol and difructosyl - mannitol with spore germination inhibiting properties. Five accessions (BRA-035726-SUGAR DRIP, BRA-035696-THEIS, BRA-036013-MN-4578, BRA-035947-MN-4418 and CMSXS-633) of sweet sorghum were selected among 50 evaluated. These five accessions failed to support secondary sporulation on the "honeydew" exuded from infected florets. There was a higher concentration (%w/v) of the free oligosaccharides on the honeydew of these accessions when compared to a hybrid male-sterile grain sorghum. Therefore, a possible strategy would be seek to incorporate a sweet character into "A" lines for hybrid seed production in order to restrict secondary disease spread.

Effect of magnesium addition on the vacancy-Mg binding free enthalpy in Al-Cr alloys

The Mg-vacancy binding free enthalpy of Al-Cr solid solution alloys with Mg addition was calculated by electrical resistivity measurements. The obtained value is lower than that obtained for dilute Al-Mg alloys with almost the same Mg content and may be attributed to the diffusion of Mg.

Design of Installation for Transport Measurements

In the present work the aim was to prepare an automatic installation for studies of galvanomagnetic effects in solids and to test it by calibration measurements. As a result required automatic installation was created in this work and test measurements were performed. Created setup automatically provides measurements of the magnetoresistance of the Hall effect with an accuracy of ± 2 µV in the temperature range 2 – 300 K and steady magnetic fields up to 6 T. The test measurements of the glassy carbon samples showed that the setup is reliable, has high sensitivity and is easy to use. The results obtained in the research process are pioneer and will be separately analyzed.

A generalized 1D particle transport method for convection diffusion reaction model

This work is devoted to the development of numerical method to deal with convection diffusion dominated problem with reaction term, non - stiff chemical reaction and stiff chemical reaction. The technique is based on the unifying Eulerian - Lagrangian schemes (particle transport method) under the framework of operator splitting method. In the computational domain, the particle set is assigned to solve the convection reaction subproblem along the characteristic curves created by convective velocity. At each time step, convection, diffusion and reaction terms are solved separately by assuming that, each phenomenon occurs separately in a sequential fashion. Moreover, adaptivities and projection techniques are used to add particles in the regions of high gradients (steep fronts) and discontinuities and transfer a solution from particle set onto grid point respectively. The numerical results show that, the particle transport method has improved the solutions of CDR problems. Nevertheless, the method is time consumer when compared with other classical technique e.g., method of lines. Apart from this advantage, the particle transport method can be used to simulate problems that involve movingsteep/smooth fronts such as separation of two or more elements in the system.

Evaluation of gas diffusion electrodes as detectors in amperometric hydrogen sensors

This work is directed to the study and evaluation of gas diffusion electrodes as detectors in hydrogen sensors. Electrochemical experiments were carried out with rotating disk electrodes with a thin porous coating of the catalyst as a previous step to select useful parameters for the sensor. An experimental arrangement made in the laboratory that simulates the sensor was found appropriate to detect volumetric hydrogen percentages above 0.25% in mixtures H2:N2. The system shows a linear response for volumetric percentages of hydrogen between 0.25 and 2 %.

Electric field measurements using scanning electron microscope

The main idea of this diploma work is to study electric field distribution on the micro level. For this purpose a silicon edgeless detector was chosen as the object of investigation and scanning electron microscope as an investigation tool. Silicon edgeless detector is an important part of installation for studying proton-proton interactions in TOTEM experiment at Large Hadron Collider. For measurement of electric field distribution inside scanning electron microscope a voltage contrast method was applied.

Harmonical oscillator and electro-mechanical analogy: an interdiscinary experiment to high precision mass variation measurements

In general, the traditional Physics courses needs examples of the aplications of the Physics concepts in other areas such as Chemistry and Biology. This lacks tend to demotivate Chemistry and Biology students regarding to deal with Physical concepts developed in classroom. In this work, the analogy among mechanic and electric oscillators is investigated to be applied in Chemistry and Biology areas, showing to be valuable due to its aplication in techniques that aims to measure mass variation with high precision. This measure could be made in a direct or indirect way. These techniques are known as electrogravimetric techniques and they are important in biosensor aplications. Thus, this paper explores the electromechanic analogy in an interdisciplinary way involving areas like Physics, Chemistry and Biology. Based on this analogy, it is proposed an experiment that can be applied in different ways, i.e. by an basic approach or more deeper, depending on the students specific formation, in other words, Physics, Chemistry or Biology.

Online Ultrasound Measurements of Membrane Compaction

There are several filtration applications in the pulp and paper industry where the capacity and cost-effectiveness of processes are of importance. Ultrafiltration is used to clean process water. Ultrafiltration is a membrane process that separates a certain component or compound from a liquid stream. The pressure difference across the membrane sieves macromolecules smaller than 0.001-0.02 μm through the membrane. When optimizing the filtration process capacity, online information about the conditions of the membrane is needed. Fouling and compaction of the membrane both affect the capacity of the filtration process. In fouling a “cake” layer starts to build on the surface of the membrane. This layer blocks the molecules from sieving through the membrane thereby decreasing the yield of the process. In compaction of the membrane the structure is flattened out because of the high pressure applied. The higher pressure increases the capacity but may damage the structure of the membrane permanently. Information about the compaction is needed to effectively operate the filters. The objective of this study was to develop an accurate system for online monitoring of the condition of the membrane using ultrasound reflectometry. Measurements of ultrafiltration membrane compaction were made successfully utilizing ultrasound. The results were confirmed by permeate flux decline, measurements of compaction with a micrometer, mechanical compaction using a hydraulic piston and a scanning electron microscope (SEM). The scientific contribution of this thesis is to introduce a secondary ultrasound transducer to determine the speed of sound in the fluid used. The speed of sound is highly dependent on the temperature and pressure used in the filters. When the exact speed of sound is obtained by the reference transducer, the effect of temperature and pressure is eliminated. This speed is then used to calculate the distances with a higher accuracy. As the accuracy or the resolution of the ultrasound measurement is increased, the method can be applied to a higher amount of applications especially for processes where fouling layers are thinner because of smaller macromolecules. With the help of the transducer, membrane compaction of 13 μm was measured in the pressure of 5 bars. The results were verified with the permeate flux decline, which indicated that compaction had taken place. The measurements of compaction with a micrometer showed compaction of 23–26 μm. The results are in the same range and confirm the compaction. Mechanical compaction measurements were made using a hydraulic piston, and the result was the same 13 μm as obtained by applying the ultrasound time domain reflectometry (UTDR). A scanning electron microscope (SEM) was used to study the structure of the samples before and after the compaction.

Diffusion of Smart Meters in Central East Europe

The present study deals with innovation diffusion as the central component of innovation process and takes smart meters as a concrete example from the electric power industry. Smart meters are seen as key enablers of the industry-wide shift towards smart grids and are recognized by the European Union as means of reaching its environmental and energy goals. However, the spread of smart meters through the market, especially in Central East Europe (CEE), is not corresponding to the expectations and identified benefits. The current work synthesizes available data for the under-researched geographical region of CEE and clarifies the process of smart meter diffusion and drivers behind it. In addition to innovation theories the methods applied are rate of adoption and thematic analysis. The results prove the large gap between optimal and actual diffusion as well as the lagging position of CEE in comparison to the EU’s market leaders. The smart metering market is driven from bottom-up and the majority of CEE countries have already carried out or started the initial activities. Therefore, in coming years more intensive smart meters deployment will be seen.

Mikkelin Pursialan pohjavesialueen haitta-aineet

Mikkelin talousvedestä kahden kolmasosan tullessa Pursialan pohjavesialueelta on alueen suojeleminen tärkeää. Pohjaveden laatua uhkaavat etenkin alueella sattuneet pohjavedenpilaantumistapaukset. Merkittävimmät pohjaveden pilaantumistapaukset ovat VAPO Oy:n sahan aiheuttama pohjaveden pilaantuminen kloorifenoleilla (CP) ja VR:n ratapölkkykyllästämön aiheuttama pohjaveden pilaantuminen kreosoottiöljyllä sekä Rinnekadun Nesteen aiheuttama pohjaveden pilaantuminen MTBE:llä. Alueella on tehty tutkimuksia ja kunnostuksia pilaantumiin liittyen, mutta näiden tuloksia ei ole aikaisemmin koottu yhteen. Tämän työn tavoitteena oli koota tulokset samaan aineistoon. Työssä keskityttiin kloorifenolien leviämisen tarkasteluun sen Pursialan pohjavedenottamolle muodostaman suurimman uhan vuoksi. Kallioperätietojen, maanpintatietojen ja näytetietojen pohjalta laadittiin myös pienoismalli CP-pilaantuman leviämisen kokonaiskuvan hahmottamiseksi. Työn tavoitteena oli lisäksi tehdä riskitarkastelua CP-pilaantumaan liittyen ja etsiä keinoja hallita havaittuja riskejä. Riskinhallintaan liittyen työssä tutkittiin kloorifenoleilla pilaantuneen alueen maaperä- ja kalliotietoja sekä pohjaveden laatutietoja. Pursialan pohjavedessä on runsaasti rautaa ja mangaania sekä aggressiivista hiilihappoa. Pohjaveden pH on alueella noin 6,5, lämpötila noin 7,5 ºC ja happipitoisuus noin 0,7 mg/l. Pursialan kaupunginalueen kallioperässä on havaittavissa VAPO Oy:n sahalta vedenottamolle etenevä kalliopainanne, jota pitkin CP etenee. Alueen kallioperä on kiillegneissiä, jossa on pohjois–etelä-suuntaista rakoilua. Maaperätuloksien perusteella on havaittavissa vettä hyvin johtavien maakerrosten jatkuminen koko vedenottamon ja sahan välisen matkan, mikä tarkoittaa, että CP-pitoisella pohjavedellä voi olla aiemmin oletettua nopeampikin yhteys sahalta vedenottamolle. Suurin CP-pitoisuus noin 100 000 µg/l on mitattu KY-5-altaan kohdalle asennetun M14-pohjavesiputken pohjasta. Talousvesiasetuksen raja-arvo CP:lle on 10 µg/l. Sahan ja vedenottamon puolivälissä on havaittu yli 10 000 µg/l meneviä CP-pitoisuuksia. Suurin vedenottamon kaivoista (kaivo 10) mitattu pitoisuus on 149 µg/l. Jakotukilta raakavedestä otetuissa näytteissä tai talousvedessä ei ole kuitenkaan havaittu talousvesiasetuksen ylittäviä CP-pitoisuuksia. Pienoismallin perusteella CP sijaitsee sahan alueella lähellä kallionpintaa ja hajaantuu koko pohjavesipatjaan vedenottamolle päin mentäessä. CP-mittaustuloksissa on havaittavissa pulssimaisuutta. Tämä johtuu todennäköisesti Saimaan pinnan vaihtelun seurauksena muuttuvasta rantaimeytyneen pohjaveden määrästä. Saimaan pinnan nousu näyttäisi tuloksien perusteella nostavan CP-pitoisuuksia saha-alueella ja laskevan lähellä vedenottamoa. Pohjaveden pintatietojen perusteella tehdyn tarkastelun mukaan pohjavesi voi kulkeutua sahalta vedenottamolle parhaimmillaan noin vuodessa. Työssä arvioitiin KY-5–liuoksen vuosittaiseksi käyttömääräksi noin 648–970 m3. Allassakkaa arvioitiin syntyneen yhteensä noin 10–31 m3. Pohjaveteen arvioitiin joutuneen toiminnan aikana yhteensä noin 3 000–4 000 kg CP:tä. Kloorifenolit esiintyvät pohjavedessä lähes täysin kloorifenolaatteina. Kloorifenolien hajoaminen ja muuntuminen pohjavedessä on epätodennäköistä. Käsitteellisen mallin mukaan kloorifenolipilaantuman suurimmat riskit aiheutuvat kloorifenolien mahdollisuudesta pilata Pursialan vedenottamon talousvesi. Tällä hetkellä riskejä hallitaan kloorifenolien leviämisen tarkkailulla, sahan ja vedenottamon puolivälissä sijaitsevalla koepumppauksella sekä varautumalla aktiivihiilijauheen syöttöön talousvesiprosessiin. Koepumppauksen avulla on saatu ylös tällä hetkellä noin 69 kg kloorifenoleita. Tutkimuksen perusteella suositeltavimmat riskinhallintatoimet tulevaisuudessa ovat sahalla sijaitseva kunnostuspumppaus, sahan ja vedenottamon väliin sijoittuva suojapumppaus- ja vesiverhoyhdistelmä sekä sahan rannan kautta tapahtuvan rantaimeytymisen estäminen.