Synthesis, characterization and chemical sensor application of conducting polymers

Polymeric materials that conduct electricity are highly interesting for fundamental studies and beneficial for modern applications in e.g. solar cells, organic field effect transistors (OFETs) as well as in chemical and bio‐sensing. Therefore, it is important to characterize this class of materials with a wide variety of methods. This work summarizes the use of electrochemistry also in combination with spectroscopic methods in synthesis and characterization of electrically conducting polymers and other π‐conjugated systems. The materials studied in this work are intended for organic electronic devices and chemical sensors. Additionally, an important part of the presented work, concerns rational approaches to the development of water‐based inks containing conducting particles. Electrochemical synthesis and electroactivity of conducting polymers can be greatly enhanced in room temperature ionic liquids (RTILs) in comparison to conventional electrolytes. Therefore, poly(para‐phyenylene) (PPP) was electrochemically synthesized in the two representative RTILs: bmimPF6 and bmiTf2N (imidazolium and pyrrolidinium‐based salts, respectively). It was found that the electrochemical synthesis of PPP was significantly enhanced in bmimPF6. Additionally, the results from doping studies of PPP films indicate improved electroactivity in bmimPF6 during oxidation (p‐doping) and in bmiTf2N in the case of reduction (n‐doping). These findings were supported by in situ infrared spectroscopy studies. Conducting poly(benzimidazobenzophenanthroline) (BBL) is a material which can provide relatively high field‐effect mobility of charge carriers in OFET devices. The main disadvantage of this n‐type semiconductor is its limited processability. Therefore in this work BBL was functionalized with poly(ethylene oxide) PEO, varying the length of side chains enabling water dispersions of the studied polymer. It was found that functionalization did not distract the electrochemical activity of the BBL backbone while the processability was improved significantly in comparison to conventional BBL. Another objective was to study highly processable poly(3,4‐ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS) water‐based inks for controlled patterning scaled‐down to nearly a nanodomain with the intention to fabricate various chemical sensors. Developed PEDOT:PSS inks greatly improved printing of nanoarrays and with further modification with quaternary ammonium cations enabled fabrication of PEDOT:PSS‐based chemical sensors for lead (II) ions with enhanced adhesion and stability in aqueous environments. This opens new possibilities for development of PEDOT:PSS films that can be used in bio‐related applications. Polycyclic aromatic hydrocarbons (PAHs) are a broad group of π‐conjugated materials consisting of aromatic rings in the range from naphthalene to even hundred rings in one molecule. The research on this type of materials is intriguing, due to their interesting optical properties and resemblance of graphene. The objective was to use electrochemical synthesis to yield relatively large PAHs and fabricate electroactive films that could be used as template material in chemical sensors. Spectroscopic, electrochemical and electrical investigations evidence formation of highly stable films with fast redox response, consisting of molecules with 40 to 60 carbon atoms. Additionally, this approach in synthesis, starting from relatively small PAH molecules was successfully used in chemical sensor for lead (II).

Paper for printed electronics and functionality

Mass-produced paper electronics (large area organic printed electronics on paper-based substrates, “throw-away electronics”) has the potential to introduce the use of flexible electronic applications in everyday life. While paper manufacturing and printing have a long history, they were not developed with electronic applications in mind. Modifications to paper substrates and printing processes are required in order to obtain working electronic devices. This should be done while maintaining the high throughput of conventional printing techniques and the low cost and recyclability of paper. An understanding of the interactions between the functional materials, the printing process and the substrate are required for successful manufacturing of advanced devices on paper. Based on the understanding, a recyclable, multilayer-coated paper-based substrate that combines adequate barrier and printability properties for printed electronics and sensor applications was developed in this work. In this multilayer structure, a thin top-coating consisting of mineral pigments is coated on top of a dispersion-coated barrier layer. The top-coating provides well-controlled sorption properties through controlled thickness and porosity, thus enabling optimizing the printability of functional materials. The penetration of ink solvents and functional materials stops at the barrier layer, which not only improves the performance of the functional material but also eliminates potential fiber swelling and de-bonding that can occur when the solvents are allowed to penetrate into the base paper. The multi-layer coated paper under consideration in the current work consists of a pre-coating and a smoothing layer on which the barrier layer is deposited. Coated fine paper may also be used directly as basepaper, ensuring a smooth base for the barrier layer. The top layer is thin and smooth consisting of mineral pigments such as kaolin, precipitated calcium carbonate, silica or blends of these. All the materials in the coating structure have been chosen in order to maintain the recyclability and sustainability of the substrate. The substrate can be coated in steps, sequentially layer by layer, which requires detailed understanding and tuning of the wetting properties and topography of the barrier layer versus the surface tension of the top-coating. A cost competitive method for industrial scale production is the curtain coating technique allowing extremely thin top-coatings to be applied simultaneously with a closed and sealed barrier layer. The understanding of the interactions between functional materials formulated and applied on paper as inks, makes it possible to create a paper-based substrate that can be used to manufacture printed electronics-based devices and sensors on paper. The multitude of functional materials and their complex interactions make it challenging to draw general conclusions in this topic area. Inevitably, the results become partially specific to the device chosen and the materials needed in its manufacturing. Based on the results, it is clear that for inks based on dissolved or small size functional materials, a barrier layer is beneficial and ensures the functionality of the printed material in a device. The required active barrier life time depends on the solvents or analytes used and their volatility. High aspect ratio mineral pigments, which create tortuous pathways and physical barriers within the barrier layer limit the penetration of solvents used in functional inks. The surface pore volume and pore size can be optimized for a given printing process and ink through a choice of pigment type and coating layer thickness. However, when manufacturing multilayer functional devices, such as transistors, which consist of several printed layers, compromises have to be made. E.g., while a thick and porous top-coating is preferable for printing of source and drain electrodes with a silver particle ink, a thinner and less absorbing surface is required to form a functional semiconducting layer. With the multilayer coating structure concept developed in this work, it was possible to make the paper substrate suitable for printed functionality. The possibility of printing functional devices, such as transistors, sensors and pixels in a roll-to-roll process on paper is demonstrated which may enable introducing paper for use in disposable “onetime use” or “throwaway” electronics and sensors, such as lab-on-strip devices for various analyses, consumer packages equipped with product quality sensors or remote tracking devices.

Komponenttien lämpöteknisten parametrien karakterisointilaitteiston suunnittelu ja toteutus

Elektroniikan pienentyessä ja tehotiheyden kasvaessa tarvitaan paremmin suunniteltuja jäähdytysjärjestelyjä. Suunnittelun apuna voidaan käyttää perinteisiä lämmönsiirtoyhtälöitä, virtauslaskentaa ja mittauksia. Tässä työssä on suunniteltu ja rakennettu mittauslaitteisto nimenomaan elektroniikan komponenttien ja jäähdytyselementtien lämpötilojen ja painehäviöiden mittaamiseen. Koeajona laitteistolla on mitattu jäähdytyselementin lämpötilajakauma kahdella eri virtausnopeudella ja lämpötilalla sekä verrattu niitä aikaisemmin mitattuihin tapauksiin sekä Fluent- virtauslaskentaohjelmalla laskettuihin tuloksiin.

Tehokerrointa korjaava skalaariohjaus puoliohjatussa ja kuusikytkintasasuuntaajassa

Verkon harmonisvirtoja rajoittavien standardien tiukentuessa joudutaan etenkin suuritehoisissa tehoelektronisissa laitteissa siirtymään aktiivisiin transistoriohjattuihin tasasuuntaajiin, jotka korjaavat tehokerrointa ja siten pienentävät verkkoon kytkeytyviä häiriövirtoja. Tässä diplomityössä esitellään yleisimpien kolmivaiheisten tasasuuntaajatopologioiden eroja ja vertaillaan puoliohjatun kolmikytkintopologian ja kuusikytkintopologian suorituskykyä tehokertoimen ja harmonissärön osalta, 16 kilowatin teholuokan taajuusmuuttajassa. Tasasuuntaajille tehtiin skalaariohjaukseen perustuva simulointimalli. Työn tavoitteena esitellään simulointitulokset harmonistason sekä tehokertoimen osalta. Työ liittyy Lappeenrannan teknillisen yliopiston sovelletun elektroniikan laboratorion ja Vacon Oyj:n yhteiseen hankkeeseen.

IGBT-simulaatiomallien soveltuvuus laitetason hyötysuhdesimulaatioihin

Tehoelektroniikkalaitteiden tehon kasvun myötä niiden hyötysuhteesta on tullut yksi niiden tärkeimmistä ominaisuuksista. Suurilla tehoilla prosentuaalisesti pienetkin tehohäviöt ovat merkittäviä ja aiheuttavat laitteen käyttäjälle ylimääräisiä energiakustannuksia ja tarvetta hukkalämmön poistolle. Näistä syistä asiakkaat vaativat hyvällä hyötysuhteella toimivia laitteita, joten laitevalmistajat pyrkivät tekemään niistä sellaisia. Simulaatiomallit ovat arvokkaita työkaluja laitesuunnittelussa. Hyötysuhdeoptimoinnin kannalta tehohäviöt tulisi pystyä mallintamaan, jotta komponenttivalintojen, ohjaustapojen ja pääpiiritopologioiden vaikutusta hyötysuhteeseen voitaisiin arvioida. Tässä työssä perehdytään eristehilabipolaaritransistorista (IGBT) tehtyihin simulaatiomalleihin ja arvioidaan niiden soveltuvuutta IGBT:ssä syntyvien tehohäviöiden mallintamiseen. Lisäksi verrataan mallia mittaukseen ja pohditaan, millaiset vaatimukset simulaatiomalliin todellisuudessa kohdistuvat.

Thermal Stress in a Roll-to-Roll Printed Electronics Substrate

The Roll-to-Roll process makes it possible to print electronic products continuously onto a uniform substrate. Printing components on flexible surfaces can bring down the costs of simple electronic devices such as RFID tags, antennas and transistors. The possibility of quickly printing flexible electronic components opens up a wide array of novel products previously too expensive to produce on a large scale. Several different printing methods can be used in Roll-to-Roll printing, such as gravure, spray, offset, flexographic and others. Most of the methods can also be mixed in one production line. Most of them still require years of research to reach a significant commercial level. The research for this thesis was carried out at the Konkuk University Flexible Display Research Center (KU-FDRC) in Seoul, Korea. A system using Roll-to-Roll printing requires that the motion of the web can be controlled in every direction in order to align different layers of ink properly. Between printers the ink is dried with hot air. The effects of thermal expansion on the tension of the web are studied in this work, and a mathematical model was constructed on Matlab and Simulink. Simulations and experiments lead to the conclusion that the thermal expansion of the web has a great influence on the tension of the web. Also, experimental evidence was gained that the particular printing machine used for these experiments at KU-FDRC may have a problem in controlling the speeds of the cylinders which pull the web.

Regioselective modification of galactose-containing polysaccharides in aqueous media

Biorefining is defined as sustainable conversion of biomass into marketable products and energy. Forests cover almost one third of earth’s land area, and account for approximately 40% of the total annual biomass production. In forest biorefining, the wood components are, in addition to the traditional paper and board products, converted into chemicals and biofuels. The major components in wood are cellulose, hemicelluloses, and lignin. The main hemicellulose in softwoods, which are of interest especially for the Nordic forest industry, is O-acetyl galactoglucomannan (GGM). GGM can be isolated in industrial scale from the waste waters of the mechanical pulping process, but is not yet today industrially utilized. In order to attain desired properties of GGM for specific end-uses, chemical and enzymatic modifications can be performed. Regioselective modifications of GGM, and other galactose-containing polysaccharides were done by oxidations, and by combining oxidations with subsequent derivatizations of the formed carbonyl or carboxyl groups. Two different pathways were investigated: activation of the C-6 positions in different sugar units by TEMPO-mediated oxidation, and activation of C-6 position in only galactose-units by oxidation catalyzed by the enzyme galactose oxidase. The activated sites were further selectively derivatized; TEMPO-oxidized GGM by a carbodiimide-mediated reaction forming amides, and GO-oxidized GGM by indium-mediated allylation introducing double or triple bonds to the molecule. In order to better understand the reaction, and to develop a MALDI-TOF-MS method for characterization of regioselectively allylated GGM, α-D-galactopyranoside and raffinose were used as model compounds. All reactions were done in aqueous media. To investigate the applicability of the modified polysaccharides for, e.g., cellulose surface functionalization, their sorption onto pulp fibres was studied. Carboxylation affects the sorption tendency significantly; a higher degree of oxidation leads to lower sorption. By controlling the degree of oxidation of the polysaccharides and the ionic strength of the sorption media, high degrees of sorption of carboxylated polysaccharides onto cellulose could, however, be obtained. Anionic polysaccharides were used as templates during laccase-catalyzed polymerization of aniline, offering a green, chemo-enzymatic route for synthesis of conducting polyaniline (PANI) composite materials. Different polysaccharide templates, such as, native GGM, TEMPO-oxidized GGM, naturally anionic κ-carrageenan, and nanofibrillated cellulose produced by TEMPO-oxidation, were assessed. The conductivity of the synthesized polysaccharide/PANI biocomposites varies depending on the polysaccharide template; κ-CGN, the anionic polysaccharide with the lowest pKa value, produces the polysaccharide/PANI biocomposites with the highest conductivity. The presented derivatization, sorption, and polymerization procedures open new application windows for polysaccharides, such as spruce GGM. The modified polysaccharides and the conducting biocomposites produced provide potential applications in biosensors, electronic devices, and tissue engineering.

Kiinteistöautomaatio osana älykkäitä sähköjärjestelmiä

Työssä tarkasteltiin älykkäiden sähköverkkojen näkökulmasta, millaisia toiminnallisuuksia kiinteistöautomaatiojärjestelmiltä odotetaan ja miten markkinoilla olevat järjestelmät vastaavat näihin odotuksiin. Lisäksi arvioitiin, kuinka taloudellisesti kannattavia valittuihin automaatiojärjestelmiin kuuluvat energian käytön hallintaan liittyvät toiminnallisuudet ovat sähkönkäyttäjien näkökulmasta. Lopuksi tehtiin lyhyt katsaus kiinteistöautomaatiojärjestelmien tulevaisuuden näkymiin. Kiinteistöautomaatiolla voidaan vaikuttaa energian käytön tehokkuuteen ohjaamalla esimerkiksi valaistusta, ilmanvaihtoa, ilmastointia, lämmitystä ja sähkölaitteita. Eräs vaihtoehto on toteuttaa ohjauksen avulla markkinapohjaista kysyntäjoustoa, jossa kiinteistön sähköjärjestelmän toimintaa säädetään sähkön hinnan perusteella. Kiinteistössä tulee myös voida tehdä laitekohtaisia energiankulutuksen mittauksia, jotka antavat tietoa sähkönkäyttäjille eri laitteiden sähkönkulutuksesta. Kiinteistöautomaation ja sähkön pientuotannon yleistymisen myötä on myös etähallittavien virtuaalivoimaloiden toteuttaminen tulossa mahdolliseksi. Lisäksi laskettiin sähkönkäyttäjän kannalta lämmityksen, valaistuksen ja ilmanvaihdon ohjauksen kannattavuutta ja selvitettiin, että tutkituissa esimerkkijärjestelmissä suurin säästöpotentiaali on lämmityksen ohjauksessa.

Pulssitettu laserablaatio mikrofluidisten kanavistojen sarjatuotantomenetelmänä

Puolijohteiden yleistyttyä vuodesta 1948 alkaen, ovat elektroniset laitteet pienentyneet jatkuvasti tehojen kuitenkin kasvaessa. Kasvaneet tehotiheydet kuitenkin vaikeuttavat laitesuunnittelua, sillä puoljohdekomponenttien suorituskyvylle ja eliniälle on oleellista lämpötilojen ja lämpötilavaihteluiden minimointi. Perinteisen ilmajäähdytyksen lähestyessä rajojaan niin kokonaistehon kuin järkevän energiatehokkuudenkin suhteen, on parhaaksi seuraavaksi teknologiaksi ennustettu kaksifaasijäähdytystä, jonka suorituskyky ja energiatehokkuus ovat vaaditulla tasolla. Kaksifaasijäähdytyksen optimaaliselle toiminnalle tärkeää on hyvin suunniteltu ja tarkasti valmistettu lämmönsiirtopinta, jota kutsutaan mikrokanavistoksi. Pulssitettu laserkaiverrus on edistynyt valmistustekniikka, jonka tarkkuus ja luotettavuus sopisivat mikrokanavistojen valmistamiseen. Laserkaiverruksella saavutettavat lopputulokset vaihtelevat kuitenkin materiaalista riippuen ja kupari – jota käytetään yleisesti lämmönjohteena – on eräs huonoimmin lasertyöstöön reagoivista materiaaleista ja siksi on oleellista selvittää laser-kaiverruksen toimivuutta kuparisten mikrokanavistojen valmistuksessa. Pulssitetun laser-kaiverruksen eri variaatioista nanosekunti-luokan pulssinpituuksilla toimivat laitteet ovat jatkuvan tuotannon kannalta paras vaihtoehto niiden hyvän tuottavuuden, saatavuuden sekä kohtuullisen alkuinvestoinnin vuoksi. Käytännön kaiverruskokeiden perusteella selvisi, että menetelmä on laatunsa ja tarkkuutensa puolesta sopiva varsinaiseen tuotantoon. Kaiverruksen tehokkuus kuparia työstettäessä on kuitenkin ennakoituakin heikompi ja niin valmistus- kuin suunnitelu-prosessikin vaativat vielä jatkotutkimusta ja -kehitystä.

A Research of Resource Scheduling Algorithm Based on Hadoop

With the development of electronic devices, more and more mobile clients are connected to the Internet and they generate massive data every day. We live in an age of “Big Data”, and every day we generate hundreds of million magnitude data. By analyzing the data and making prediction, we can carry out better development plan. Unfortunately, traditional computation framework cannot meet the demand, so the Hadoop would be put forward. First the paper introduces the background and development status of Hadoop, compares the MapReduce in Hadoop 1.0 and YARN in Hadoop 2.0, and analyzes the advantages and disadvantages of them. Because the resource management module is the core role of YARN, so next the paper would research about the resource allocation module including the resource management, resource allocation algorithm, resource preemption model and the whole resource scheduling process from applying resource to finishing allocation. Also it would introduce the FIFO Scheduler, Capacity Scheduler, and Fair Scheduler and compare them. The main work has been done in this paper is researching and analyzing the Dominant Resource Fair algorithm of YARN, putting forward a maximum resource utilization algorithm based on Dominant Resource Fair algorithm. The paper also provides a suggestion to improve the unreasonable facts in resource preemption model. Emphasizing “fairness” during resource allocation is the core concept of Dominant Resource Fair algorithm of YARM. Because the cluster is multiple users and multiple resources, so the user’s resource request is multiple too. The DRF algorithm would divide the user’s resources into dominant resource and normal resource. For a user, the dominant resource is the one whose share is highest among all the request resources, others are normal resource. The DRF algorithm requires the dominant resource share of each user being equal. But for these cases where different users’ dominant resource amount differs greatly, emphasizing “fairness” is not suitable and can’t promote the resource utilization of the cluster. By analyzing these cases, this thesis puts forward a new allocation algorithm based on DRF. The new algorithm takes the “fairness” into consideration but not the main principle. Maximizing the resource utilization is the main principle and goal of the new algorithm. According to comparing the result of the DRF and new algorithm based on DRF, we found that the new algorithm has more high resource utilization than DRF. The last part of the thesis is to install the environment of YARN and use the Scheduler Load Simulator (SLS) to simulate the cluster environment.

Performance Analysis of IP based WSNs in real time systems

Wireless sensor networks (WSNs) are the key enablers of the internet of things (IoT) paradigm. Traditionally, sensor network research has been to be unlike the internet, motivated by power and device constraints. The IETF 6LoWPAN draft standard changes this, defining how IPv6 packets can be efficiently transmitted over IEEE 802.15.4 radio links. Due to this 6LoWPAN technology, low power, low cost micro- controllers can be connected to the internet forming what is known as the wireless embedded internet. Another IETF recommendation, CoAP allows these devices to communicate interactively over the internet. The integration of such tiny, ubiquitous electronic devices to the internet enables interesting real-time applications. This thesis work attempts to evaluate the performance of a stack consisting of CoAP and 6LoWPAN over the IEEE 802.15.4 radio link using the Contiki OS and Cooja simulator, along with the CoAP framework Californium (Cf). Ultimately, the implementation of this stack on real hardware is carried out using a raspberry pi as a border router with T-mote sky sensors as slip radios and CoAP servers relaying temperature and humidity data. The reliability of the stack was also demonstrated during scalability analysis conducted on the physical deployment. The interoperability is ensured by connecting the WSN to the global internet using different hardware platforms supported by Contiki and without the use of specialized gateways commonly found in non IP based networks. This work therefore developed and demonstrated a heterogeneous wireless sensor network stack, which is IP based and conducted performance analysis of the stack, both in terms of simulations and real hardware.