Interfacial effects in organic solar cells

Solceller baserade på organiska halvledare erbjuder en möjlighet till storskalig och billig solenergiproduktion. Organiska halvledare har den fördelen att de är lösningsprocesserbara vilket gör att solceller och andra elektroniska komponenter baserade på dessa halvledare kan tillverkas vid låga temperaturer och med liten energiförbrukning. Nackdelen med dessa material är deras strukturella och energetiska oordning som leder till lägre effektivitet. För att organiska solceller ska kunna kommersialiseras krävs grundläggande insikter i de olika processer som begränsar effektiviteten. En stor del av forskningen om dessa processer har varit fokuserad kring egenskaperna av solcellens olika komponenter (de aktiva materialen) som sådana, medan gränsytorna mellan olika material har fått mindre uppmärksamhet. Gränsytor mellan olika material har distinkt olika egenskaper jämfört med ett rent material, och gränsytors olika egenskaper kan ha en väldigt stor inverkan på hur solcellerna fungerar. Syftet med denna avhandling är att klargöra några olika gränsyterelaterade effekter i organiska dioder och solceller. De gränsytor som behandlas är gränsytan mellan kontakten och det aktiva lagret (metall-organisk) och gränsytan mellan donor och acceptor (organisk-organisk). Resultaten visar att metall-organiska gränsytor måste designas noggrant för att begränsa förlust av effektivitet. En icke-idealisk kontakt leder till starkt reducerad effektivitet på grund av att elektronerna extraheras ineffektivt. Även till synes idealiska kontakter kan orsaka förluster genom spontan laddningsöverföring från metallen till det organiska lagret som effektivt sett minskar på den spänning som cellen kan alstra. Den organisk-organiska gränsytan påverkar hur mycket ström cellen kan alstra och beroende på gränsytans beskaffenhet kan de negativa rekombinationsprocesserna i materialet kontrolleras. ------------------------------------------------- Orgaanisille puolijohteille perustuvat aurinkokennot mahdollistavat suurimuotoisen ja edullisen aurinkoenergiatuotannon. Orgaanisten puolijohteiden etu on että ne voidaan liuottaa, jolloin aurinkokennot ja muut näille johteille perustuvat elektroniset komponentit voidaan valmistaa alhaisessa lämpötilassa kuluttaen vähän energiaa. Materiaalien huonona puolena on kuitenkin niiden rakenteellinen ja energeettinen epäjärjestys, jonka seurauksena niiden tehokkuus on huonompi. Orgaanisten aurinkokennojen kaupallistaminen edellyttää perustavanlaatuista ymmärystä tehokkuutta rajoittavista prosesseista. Aurinkokennotutkimus on pääosin keskittynyt aurinkokennon eri komponenttien (aktiivisten materiaalien) ominaisuuksiin, kun taas eri materiaalien rajapinnat ovat jääneet vähemmälle huomiolle. Eri materiaalien välisillä rajapinnoilla on huomattavan erilaisia ominaisuuksia verrattuna puhtaisiin materiaaleihin. Rajapintojen ominaisuudet voivat kuitenkin vaikuttaa merkittävästi aurinkokennojen toimintaan. Tämän väitöstutkimuksen tarkoituksena on selventää joitain rajapintoihin liittyviä toimintoja orgaanisissa diodeissa ja aurinkokennoissa. Käsiteltävät rajapinnat ovat rajapinta kontaktin ja aktiivisen kerroksen välillä (metallis-orgaaninen) ja rajapinta donorin ja akseptorin välillä (orgaanis-orgaaninen). Tutkimustulokset osoittavat, että metallis-orgaaniset rajapinnat tulee suunnitella huolellisesti, jotta tehokkuuden alenemista voidaan rajoittaa. Mikäli kontakti ei ole ideaalisti suunniteltu, vähenee tehokkuus huomattavasti, mikä johtuu elektronien tehottomasta ekstrahoinnista. Jopa ideaalisilta vaikuttavat kontaktit voivat johtaa tehokkuuden alenemiseen, mikäli varaus siirtyy spontaanisti metallista orgaaniseen kerrokseen, sillä tämä alentaa jännitettä jonka kenno voi tuottaa. Kennon orgaanis-orgaaninen rajapinta vaikuttaa siihen, kuinka paljon virtaa kenno pystyy tuottamaan. Rajapinnan ominaisuuksista riippuen materiaalin rekombinaatio on hallittavissa.

Implementation of population balances in simulation of gas-liquid reactors using a CFD-PBM coupled approach

In bubbly flow simulations, bubble size distribution is an important factor in determination of hydrodynamics. Beside hydrodynamics, it is crucial in the prediction of interfacial area available for mass transfer and in the prediction of reaction rate in gas-liquid reactors such as bubble columns. Solution of population balance equations is a method which can help to model the size distribution by considering continuous bubble coalescence and breakage. Therefore, in Computational Fluid Dynamic simulations it is necessary to couple CFD and Population Balance Model (CFD-PBM) to get reliable distribution. In the current work a CFD-PBM coupled model is implemented as FORTRAN subroutines in ANSYS CFX 10 and it has been tested for bubbly flow. This model uses the idea of Multi Phase Multi Size Group approach which was previously presented by Sha et al. (2006) [18]. The current CFD-PBM coupled method considers inhomogeneous flow field for different bubble size groups in the Eulerian multi-dispersed phase systems. Considering different velocity field for bubbles can give the advantageof more accurate solution of hydrodynamics. It is also an improved method for prediction of bubble size distribution in multiphase flow compared to available commercial packages.

Gas-liquid mass transfer in bubbly flow: Estimation of mass transfer, bubble size and reactor performance in various applications

Gas-liquid mass transfer is an important issue in the design and operation of many chemical unit operations. Despite its importance, the evaluation of gas-liquid mass transfer is not straightforward due to the complex nature of the phenomena involved. In this thesis gas-liquid mass transfer was evaluated in three different gas-liquid reactors in a traditional way by measuring the volumetric mass transfer coefficient (kLa). The studied reactors were a bubble column with a T-junction two-phase nozzle for gas dispersion, an industrial scale bubble column reactor for the oxidation of tetrahydroanthrahydroquinone and a concurrent downflow structured bed.The main drawback of this approach is that the obtained correlations give only the average volumetric mass transfer coefficient, which is dependent on average conditions. Moreover, the obtained correlations are valid only for the studied geometry and for the chemical system used in the measurements. In principle, a more fundamental approach is to estimate the interfacial area available for mass transfer from bubble size distributions obtained by solution of population balance equations. This approach has been used in this thesis by developing a population balance model for a bubble column together with phenomenological models for bubble breakage and coalescence. The parameters of the bubble breakage rate and coalescence rate models were estimated by comparing the measured and calculated bubble sizes. The coalescence models always have at least one experimental parameter. This is because the bubble coalescence depends on liquid composition in a way which is difficult to evaluate using known physical properties. The coalescence properties of some model solutions were evaluated by measuring the time that a bubble rests at the free liquid-gas interface before coalescing (the so-calledpersistence time or rest time). The measured persistence times range from 10 msup to 15 s depending on the solution. The coalescence was never found to be instantaneous. The bubble oscillates up and down at the interface at least a coupleof times before coalescence takes place. The measured persistence times were compared to coalescence times obtained by parameter fitting using measured bubble size distributions in a bubble column and a bubble column population balance model. For short persistence times, the persistence and coalescence times are in good agreement. For longer persistence times, however, the persistence times are at least an order of magnitude longer than the corresponding coalescence times from parameter fitting. This discrepancy may be attributed to the uncertainties concerning the estimation of energy dissipation rates, collision rates and mechanisms and contact times of the bubbles.

Fibre-reinforced composites as root canal posts

Fibre-reinforced composite (FRC) root canal posts are suggested to have biomechanical benefits over traditional metallic posts, but they lack good adhesion to resin composites. The aim of this series of studies was to evaluate the adhesion of individually formed fibre-reinforced composite material to composite resin and dentin, as well as some mechanical properties. Flexural properties were evaluated and compared between individually formed FRC post material and different prefabricated posts. The depth of polymerization of the individually formed FRC post material was evaluated with IR spectrophotometry and microhardness measurements, and compared to that of resin without fibres. Bonding properties of the individually formed FRC post to resin cements and dentin were tested using Pull-out- and Push-out-force tests, evaluated with scanning electron microscopy, and compared to those of prefabricated FRC and metal posts. Load-bearing capacity and microstrain were evaluated and failure mode assessment was made on incisors restored with individually formed FRC posts of different structures and prefabricated posts. The results of these studies show that the individually polymerized and formed FRC post material had higher flexural properties compared to the commercial prefabricated FRC posts. The individually polymerized FRC material showed almost the same degree of conversion after light polymerization as monomer resin without fibres. Moreover, it was found that the individually formed FRC post material with a semiinterpenetrating polymer network (IPN) polymer matrix bonded better to composite resin luting cement, than did the prefabricated posts with a cross-linked polymer matrix. Furthermore, it was found that, contrary to the other posts, there were no adhesive failures between the individually formed FRC posts and composite resin luting cement. This suggests better interfacial adhesion of cements to these posts. Although no differences in load-bearing capacity or microstrain could be seen, the incisors restored with individually formed FRC posts with a hollow structure showed more favourable failures compared to other prefabricated posts. These studies suggest that it is possible to use individually formed FRC material with semi-IPN polymer matrix as root canal post material. They also indicate that there are benefits especially regarding the bonding properties to composite resin and dentin with this material compared to prefabricated FRC post material with a cross-linked matrix. Furthermore, clinically more repairable failures were found with this material compared to those of prefabricated posts.

Synteesikaasun liukoisuus ja aineensiirto fermentointiliuokseen

Työssä tutkittiin synteesikaasun komponenttien: hiilimonoksidin, vedyn ja hiilidioksidin liukoisuutta ja aineensiirtonopeutta fermentointiliuokseen. Kirjallisuusosassa käsitellään kaasujen liukoisuuksiin ja kaasu-nesteaineensiirtoon vaikuttavia tekijöitä ja esitellään korrelaatioita, jotka on kehitetty volumetrisen aineensiirtokertoimen ennustamiseen sekoitetussa fermentorissa. Kirjallisuus-osassa esitetään myös synteesikaasun komponenttien liukoisuudet veteen, etanoliin ja etikkahappoon 37 ºC lämpötilassa ja esitellään Flowbat-simulointiohjelman MHV2-mallin käyttöä kaasu-neste tasapainojen mallin-nuksessa. Työn kokeellisessa osassa tutkittiin synteesikaasun komponenttien liukoisuuksia veteen ja kasvatusalustaan sekä kehitettiin mittausmenetelmä kaasu-neste tasapainojen mittaukseen. Tasapainomittauksissa tutkittiin etanolin ja etikkahapon konsentraatioiden vaikutusta synteesikaasun liukoisuuteen. Lisäksi mallinnettiin kaasu-neste tasapainoja monikomponenttisysteemeissä MHV2-mallin avulla. Kokeellisen osan aineensiirtomittauksissa tutkittiin sekoitusnopeuden ja kaasun volumetrisen syöttönopeuden vaikutusta hiilimonoksidin ja vedyn volumetriseen aineensiirtokertoimeen kLa kahden litran tilavuuksisessa laboratoriofermentorissa. Mittaustulosten perusteella kasvatusalustan komponentit vaikuttavat merkittävästi hiilidioksidin liukoisuuteen. Lisäys etanolin ja etikkahapon konsentraatioissa parantaa hiilimonoksidin liukoisuutta kasvatusalustaan. Kaasun volumetrinen syöttönopeus ja sekoitusnopeus vaikuttavat voimakkaasti volumetrisen aineensiirtokertoimen arvoon. Tutkitussa systeemissä korkein teoreettinen solutiheys, joka voitiin saavuttaa suurimmalla hiilimonoksidin aineensiirto-nopeudella, oli 3 g/L. Tämä on kaksinkertainen verrattuna aiemmissa VTT:n kokeissa saavutettuihin solutiheyksiin.

Studies of Liquid-liquid Separation in Fibre Coalescer

This thesis focuses on fibre coalescers whose efficiency is based on the surface properties/characteristics. They have the ability to preferentially wet or interact with one or more of the fluids to be separated. Thus, the interfacial phenomena governing the separation efficiency of the coalescers is investigated depending on physical factors such as flowrates, phase ratios and coalescer packing density. Design of process equipment to produce and separate of the emulsions was carried out.The experimentation was carried out to test the separation efficiency of the coalescing medias, namely fibreglass, polyester I and polyester II. The performances of the coalescing medias were assessed via droplet size information. In conclusion, the objectives (design of process equipment and experimentation) were achieved. Fibre glass was the best coalescing media, next was polyester I and then finally polyester II. Droplets sizes increased with decreased flowrates and increased packing density of the coalescer. Phase ratio had effect on the droplet sizes of the feed but had no effect on the coalescence of droplets of the feed.

Uutto-olosuhteiden vaikutus kasviperäisen indigon saantoon

Indigo on väriaine, jota valmistetaan petrokemianteollisuuden välituotteena syntyvästä aniliinista. Indigolla on kuitenkin pitkä historia. Sitä on valmistettu perinteisesti eri viljelykasveista, joista Euroopassa merkittävin on ollut morsinko. Luonnonmukaisten tuotteiden suosion kasvaessa on ryhdytty selvittämään morsingon viljelyn potentiaalia. Viljelyn kannattavuuden kannalta olennaista on kasvin lehdissä esiintyvien indigon esiasteiden mahdollisimman täydellinen eristäminen. Indigoa tuotetaan uuttamalla indigon esiasteet veteen. Esiasteet hajoavat synnyttäen indoksyyliä, josta hapen vaikutuksella muodostuu indigoa. Syntynyt indigo saostuu ja laskeutuu pohjalle. Samalla kuitenkin tapahtuu epätoivottuja sivureaktioita, jotka vähentävät indigon saantoa. Tutkimuksen tavoitteena oli laboratorio- ja kenttäkokeiden avulla löytää indigon saantoa parantavat uutto-olosuhteet. Kokeiden perusteella havaittiin, että indigon saantoon vaikuttavat positiivisesti pH:n laskeminen, lämpötilan nostaminen, morsingon lehtien pilkkominen ja uuttoliuoksen sekoittaminen. Uuttoliuoksen suolapitoisuuden havaittiin puolestaan vaikuttavan indigon saantoon negatiivisesti. Laboratoriokokeiden perusteella havaittu pH:n laskemisen vaikutus indigon saantoon todistettiin myös kenttäolosuhteissa. Kokeiden havaintojen perusteella esitettiin olosuhteiden indigosaantoa parantavien vaikutusten johtuvan kahdesta tekijästä: indoksyylin stabiloitumisesta happamassa ympäristössä, jolloin sivureaktioiden osuus vähenee, sekä aineensiirron paranemisella sekoituksen, faasien rajapinnan kasvamisen ja etenkin lehtien vahakerroksen rikkoutumisen kuuman veden ja hapon vaikutuksesta.

Improving the calculation of rate of stratification in APROS

APROS (Advanced Process Simulation Environment) is a computer simulation program developed to simulate thermal hydraulic processes in nuclear and conventional power plants. Earlier research at VTT Technological Research Centre of Finland had found the current version of APROS to produce inaccurate simulation results for a certain case of loop seal clearing. The objective of this Master’s thesis is to find and implement an alternative method for calculating the rate of stratification in APROS, which was found to be the reason for the inaccuracies. Brief literature study was performed and a promising candidate for the new method was found. The new method was implemented into APROS and tested against experiments and simulations from two test facilities and the current version of APROS. Simulation results with the new version were partially conflicting; in some cases the new method was more accurate than the current version, in some the current method was better. Overall, the new method can be assessed as an improvement.

Kytkentäaineet puumuovikomposiiteissa

Puumuovikomposiittien valmistuksessa yhdistetään kaksi toisistaan eroavaa materiaalia jolloin saadaan aikaan materiaalien ominaisuuksien ainutlaatuinen yhdistelmä. Polymeerimateriaaleina käytetään pääasiassa erilaisia kestomuoveja. Kuitumateriaaleina voidaan käyttää puujauhetta, sahanpurua, paperin- ja kartongin valmistuksessa käytettävää sellua, nanoselluloosaa tai muita puukuitumateriaaleja. Polaarisen puukuidun ja polaarittoman muovimateriaalin välinen materiaalien rajapinnan adheesio on yleensä riittämätöntä, mikä vaikuttaa lopputuotteen ominaisuuksien heikkenemiseen. Kyseinen ongelma on pyritty ratkaisemaan käyttämällä erilaisia kytkentäaineita. Tässä työssä keskitytään käsittelemään erilaisia puumuovikomposiittien kytkentäaineita, niiden toimintaa sekä vaikutuksia lopputuotteeseen. Lisäksi työssä esitellään myös puumuovikomposiittien valmistusmateriaaleja ja valmistusprosesseja.

Model-based estimation of liquid flows in the blast furnace hearth and taphole

This thesis presents a set of methods and models for estimation of iron and slag flows in the blast furnace hearth and taphole. The main focus was put on predicting taphole flow patterns and estimating the effects of various taphole conditions on the drainage behavior of the blast furnace hearth. All models were based on a general understanding of the typical tap cycle of an industrial blast furnace. Some of the models were evaluated on short-term process data from the reference furnace. A computational fluid dynamics (CFD) model was built and applied to simulate the complicated hearth flows and thus to predict the regions of the hearth exerted to erosion under various operating conditions. Key boundary variables of the CFD model were provided by a simplified drainage model based on the first principles. By examining the evolutions of liquid outflow rates measured from the furnace studied, the drainage model was improved to include the effects of taphole diameter and length. The estimated slag delays showed good agreement with the observed ones. The liquid flows in the taphole were further studied using two different models and the results of both models indicated that it is more likely that separated flow of iron and slag occurs in the taphole when the liquid outflow rates are comparable during tapping. The drainage process was simulated with an integrated model based on an overall balance analysis: The high in-furnace overpressure can compensate for the resistances induced by the liquid flows in the hearth and through the taphole. Finally, a recently developed multiphase CFD model including interfacial forces between immiscible liquids was developed and both the actual iron-slag system and a water-oil system in laboratory scale were simulated. The model was demonstrated to be a useful tool for simulating hearth flows for gaining understanding of the complex phenomena in the drainage of the blast furnace.

Development of a process for the direct synthesis of hydrogen peroxide in a novel microstructured reactor

Microreactors have proven to be versatile tools for process intensification. Over recent decades, they have increasingly been used for product and process development in chemical industries. Enhanced heat and mass transfer in the reactors due to the extremely high surfacearea- to-volume ratio and interfacial area allow chemical processes to be operated at extreme conditions. Safety is improved by the small holdup volume of the reactors and effective control of pressure and temperature. Hydrogen peroxide is a powerful green oxidant that is used in a wide range of industries. Reduction and auto-oxidation of anthraquinones is currently the main process for hydrogen peroxide production. Direct synthesis is a green alternative and has potential for on-site production. However, there are two limitations: safety concerns because of the explosive gas mixture produced and low selectivity of the process. The aim of this thesis was to develop a process for direct synthesis of hydrogen peroxide utilizing microreactor technology. Experimental and numerical approaches were applied for development of the microreactor. Development of a novel microreactor was commenced by studying the hydrodynamics and mass transfer in prototype microreactor plates. The prototypes were designed and fabricated with the assistance of CFD modeling to optimize the shape and size of the microstructure. Empirical correlations for the mass transfer coefficient were derived. The pressure drop in micro T-mixers was investigated experimentally and numerically. Correlations describing the friction factor for different flow regimes were developed and predicted values were in good agreement with experimental results. Experimental studies were conducted to develop a highly active and selective catalyst with a proper form for the microreactor. Pd catalysts supported on activated carbon cloths were prepared by different treatments during the catalyst preparation. A variety of characterization methods were used for catalyst investigation. The surface chemistry of the support and the oxidation state of the metallic phase in the catalyst play important roles in catalyst activity and selectivity for the direct synthesis. The direct synthesis of hydrogen peroxide was investigated in a bench-scale continuous process using the novel microreactor developed. The microreactor was fabricated based on the hydrodynamic and mass transfer studies and provided a high interfacial area and high mass transfer coefficient. The catalysts were prepared under optimum treatment conditions. The direct synthesis was conducted at various conditions. The thesis represents a step towards a commercially viable direct synthesis. The focus is on the two main challenges: mitigating the safety problem by utilization of microprocess technology and improving the selectivity by catalyst development.

Computational studies for the design of process equipment with complex geometries

This study combines several projects related to the flows in vessels with complex shapes representing different chemical apparata. Three major cases were studied. The first one is a two-phase plate reactor with a complex structure of intersecting micro channels engraved on one plate which is covered by another plain plate. The second case is a tubular microreactor, consisting of two subcases. The first subcase is a multi-channel two-component commercial micromixer (slit interdigital) used to mix two liquid reagents before they enter the reactor. The second subcase is a micro-tube, where the distribution of the heat generated by the reaction was studied. The third case is a conventionally packed column. However, flow, reactions or mass transfer were not modeled. Instead, the research focused on how to describe mathematically the realistic geometry of the column packing, which is rather random and can not be created using conventional computeraided design or engineering (CAD/CAE) methods. Several modeling approaches were used to describe the performance of the processes in the considered vessels. Computational fluid dynamics (CFD) was used to describe the details of the flow in the plate microreactor and micromixer. A space-averaged mass transfer model based on Fick’s law was used to describe the exchange of the species through the gas-liquid interface in the microreactor. This model utilized data, namely the values of the interfacial area, obtained by the corresponding CFD model. A common heat transfer model was used to find the heat distribution in the micro-tube. To generate the column packing, an additional multibody dynamic model was implemented. Auxiliary simulation was carried out to determine the position and orientation of every packing element in the column. This data was then exported into a CAD system to generate desirable geometry, which could further be used for CFD simulations. The results demonstrated that the CFD model of the microreactor could predict the flow pattern well enough and agreed with experiments. The mass transfer model allowed to estimate the mass transfer coefficient. Modeling for the second case showed that the flow in the micromixer and the heat transfer in the tube could be excluded from the larger model which describes the chemical kinetics in the reactor. Results of the third case demonstrated that the auxiliary simulation could successfully generate complex random packing not only for the column but also for other similar cases.

Membrane properties of structurally modified ceramides : effects on lipid lateral distribution and sphingomyelin-interactions in artificial bilayer membranes

Ceramides comprise a class of sphingolipids that exist only in small amounts in cellular membranes, but which have been associated with important roles in cellular signaling processes. The influences that ceramides have on the physical properties of bilayer membranes reach from altered thermodynamical behavior to significant impacts on the molecular order and lateral distribution of membrane lipids. Along with the idea that the membrane physical state could influence the physiological state of a cell, the membrane properties of ceramides have gained increasing interest. Therefore, membrane phenomena related to ceramides have become a subject of intense study both in cellular as well as in artificial membranes. Artificial bilayers, the so called model membranes, are substantially simpler in terms of contents and spatio-temporal variation than actual cellular membranes, and can be used to give detailed information about the properties of individual lipid species in different environments. This thesis focuses on investigating how the different parts of the ceramide molecule, i.e., the N-linked acyl chain, the long-chain sphingoid base and the membrane-water interface region, govern the interactions and lateral distribution of these lipids in bilayer membranes. With the emphasis on ceramide/sphingomyelin(SM)-interactions, the relevance of the size of the SMhead group for the interaction was also studied. Ceramides with methylbranched N-linked acyl chains, varying length sphingoid bases, or methylated 2N (amide-nitrogen) and 3O (C3-hydroxyl) at the interface region, as well as SMs with decreased head group size, were synthesized and their bilayer properties studied by calorimetric and fluorescence spectroscopic techniques. In brief, the results showed that the packing of the ceramide acyl chains was more sensitive to methyl-branching in the mid part than in the distal end of the N-linked chain, and that disrupting the interfacial structure at the amide-nitrogen, as opposed to the C3-hydroxyl, had greater effect on the interlipid interactions of ceramides. Interestingly, it appeared that the bilayer properties of ceramides could be more sensitive to small alterations in the length of the long-chain base than what was previously reported for the N-linked acyl chain. Furthermore, the data indicated that the SM-head group does not strongly influence the interactions between SMs and ceramides. The results in this thesis illustrate the pivotal role of some essential parts of the ceramide molecules in determining their bilayer properties. The thesis provides increased understanding of the molecular aspects of ceramides that possibly affect their functions in biological membranes, and could relate to distinct effects on cell physiology.

Reducing contact resistance in graphene devices

In this thesis, the contact resistance of graphene devices was investigated because high contact resistance is detrimental to the performance of graphene field-effect transistors (GFET). Method for increasing so-called edge-contact area was applied in device fabrication process, as few nanometers thick Ni layer was used as a catalytic etchant during the annealing process. Finally, Ni was also used as a metal for contact. GFETs were fabricated using electron beam lithography using graphene fabricated by chemical vapor deposition (CVD). Critical part of the fabrication process was to preserve the high quality of the graphene channel while etching the graphene at contact areas with Ni during the annealing. This was achieved by optimizing the combination of temperature and gas flows. The structural properties of graphene were studied using scanning electron microscopy, scanning confocal μ-Raman spectroscopy and optical microscopy. Evaluation of electric transport properties including contact resistance was carried out by transmission line method and four-probe method. The lowest contact resistance found was about at 350 Ωμm. In addition, different methods to transfer CVD graphene synthesized on copper were studied. Typical method using PMMA as a supporting layer leaves some residues after its removal, thus effecting on the performance of a graphene devices. In a metal assisted transfer method, metal is used as an interfacial layer between PMMA and graphene. This allows more effective removal of PMMA. However, Raman spectra of graphene transferred by metal assisted method showed somewhat lower quality than the PMMA assisted method

Catalytic direct synthesis of hydrogen peroxide in a novel microstructured reactor

The direct synthesis from hydrogen and oxygen is a green alternative for production of hydrogen peroxide. However, this process suffers from two challenges. Firstly, mixtures of hydrogen and oxygen are explosive over a wide range of concentrations (4-94% H2 in O2). Secondly, the catalytic reaction of hydrogen and oxygen involves several reaction pathways, many of them resulting in water production and therfore decreasing selectivity. The present work deals with these two challenges. The safety problem was dealed by employing a novel microstructured reactor. Selectivity of the reaction was highly improved by development a set of new catalysts. The final goal was to develop an effective and safe continuous process for direct synthesis of hydrogen peroxide from H2 and O2. Activated carbon cloth and Sibunit were examined as the catalysts’ supports. Palladium and gold monometallic and palladium-gold bimetallic catalysts were thoroughly investigated by numerous kinetic experiments performed in a tailored batch reactor and several catalyst charachterization methods. A complete set of data for direct synthesis of H2O2 and its catalytic decomposition and hydrogenation was obtained. These data were used to assess factors influencing selectivity and activity of the catalysts in direct synthesis of H2O2 as well as its decomposition and hydrogenation. A novel microstructured reactor was developed based on hydrodynamics and mass transfer studies in prototype microstractural plates. The shape and the size of the structural elements in the microreactor plate were optimized in a way to get high gas-liquid interfacial area and gas-liquid mass transfer. Finally, empirical correlations for the volumetric mass transfer coefficient were derived. A bench-scale continuous process was developed by using the novel microstructral plate reactor. A series of kinetic experiments were performed to investigate the effects of the gas and the liquid feed rates and their ratio, the amount of the catalyst, the gas feed composition and pressure on the final rate of H2O2 production and selectivity.