Electrical and dielectric properties of uncoated and coated wood-free paper for electrophotography

The print substrate influences the print result in dry toner electrophotography, which is a widely used digital printing method. The influence of the substrate can be seen more easily in color printing, as that is a more complex process compared to monochrome printing. However, the print quality is also affected by the print substrate in grayscale printing. It is thus in the interests of both substrate producers and printing equipment manufacturers to understand the substrate properties that influence the quality of printed images in more detail. In dry toner electrophotography, the image is printed by transferring charged toner particles to the print substrate in the toner transfer nip, utilizing an electric field, in addition to the forces linked to the contact between toner particles and substrate in the nip. The toner transfer and the resulting image quality are thus influenced by the surface texture and the electrical and dielectric properties of the print substrate. In the investigation of the electrical and dielectric properties of the papers and the effects of substrate roughness, in addition to commercial papers, controlled sample sets were made on pilot paper machines and coating machines to exclude uncontrolled variables from the experiments. The electrical and dielectric properties of the papers investigated were electrical resistivity and conductivity, charge acceptance, charge decay, and the dielectric permittivity and losses at different frequencies, including the effect of temperature. The objective was to gain an understanding of how the electrical and dielectric properties are affected by normal variables in papermaking, including basis weight, material density, filler content, ion and moisture contents, and coating. In addition, the dependency of substrate resistivity on the electric field applied was investigated. Local discharging did not inhibit transfer with the paper roughness levels that are normal in electrophotographic color printing. The potential decay of paper revealed that the charge decay cannot be accurately described with a single exponential function, since in charge decay there are overlapping mechanisms of conduction and depolarization of paper. The resistivity of the paper depends on the NaCl content and exponentially on moisture content although it is also strongly dependent on the electric field applied. This dependency is influenced by the thickness, density, and filler contents of the paper. Furthermore, the Poole-Frenkel model can be applied to the resistivity of uncoated paper. The real part of the dielectric constant ε’ increases with NaCl content and relative humidity, but when these materials cannot polarize freely, the increase cannot be explained by summing the effects of their dielectric constants. Dependencies between the dielectric constant and dielectric loss factor and NaCl content, temperature, and frequency show that in the presence of a sufficient amount of moisture and NaCl, new structures with a relaxation time of the order of 10-3 s are formed in paper. The ε’ of coated papers is influenced by the addition of pigments and other coating additives with polarizable groups and due to the increase in density. The charging potential decreases and the electrical conductivity, potential decay rate, and dielectric constant of paper increase with increasing temperature. The dependencies are exponential and the temperature dependencies and their activation energies are altered by the ion content. The results have been utilized in manufacturing substrates for electrophotographic color printing.

Negative refractive index materials and propagation

Negative refractive index materials and propagation of electromagnetic waves in them started to draw attention of scientists not so long ago. This review highlights historically important and recent papers on practical and theoretical aspects related to these issues. Namely, basic properties and peculiarities of such materials related to both their design and wave propagation in them, experimental verification of predictions theoretically made for them, possible practical applications and prospects in this area are considered.

Kelvin Probe Force Microscopy (KPFM) characterization of lanthanum lutetium oxide high-k dielectric thin films

Lanthanum lutetium oxide (LaLuO3) thin films were investigated considering their perspective application for industrial microelectronics. Scanning probe microscopy (SPM) techniques permitted to visualize the surface topography and study the electric properties. This work compared both the material properties (charge behavior for samples of 6 nm and 25 nm width) and the applied SPM modes. Particularly, Kelvin probe force microscopy (KPFM) was applied to characterize local potential difference with high lateral resolution. Measurements showed the difference in morphology, chargeability and charge dissipation time for both samples. The polarity effect was detected for this material for the first time. Lateral spreading of the charged spots indicate the diffusive mechanism to be predominant in charge dissipation. This allowed to estimate the diffusion coefficient and mobility. Using simple electrostatic model it was found that charge is partly leaking into the interface oxide layer.

Mikroliuskarakenteisen T-resonaattorin käyttö piirilevyn eristeominaisuuksien määrityksessä

Tässä diplomityössä tutkittiin ja kehitettiin edelleen mikroliuskarakenteisen T-resonaattorin käyttöä laajakaistaisessa piirilevylaminaattien dielektrisyysvakion ja häviökertoimen määrityksessä. Työssä perehdyttiin eristeominaisuuksien määrityksessä tarvittaviin laskentamenetelmiin sekä T-resonaattorin toimintaan. T-resonaattorin suunnittelu ja käyttöä varten valitut laskentamenetelmät on esitelty. Työssä suunniteltiin ja valmistettiin mikroliuskarakenteinen T-resonaattorimittausrakenne, jolla määritettiin erään FR-4 -tyyppisen piirilevylaminaattimateriaalin dielektrisyysvakio sekä häviökerroin mittausten ja laskennan avulla taajuuskaistalla 0,5 - 10 GHz. Tuloksia verrattiin muilla käytössä olevilla menetelmillä määritettyihin tuloksiin. Tulosten perusteella voitiin osoittaa, että mikroliuskarakenteinen T-resonaattori soveltuu hyvin piirilevylaminaattien eristeominaisuuksien määritykseen, ja käytetyt laskenta-menetelmät antavat realistisia tuloksia.

Alikriittisen veden käyttö kromatografisessa erotuksessa

Alikriittisellä vedellä tarkoitetaan paineistettua vettä, joka on kriittisen lämpötilansa (374 °C) alapuolella nestemäisessä tilassa. Veden tiheys pienenee lämpötilan kasvaessa Veden liuotinominaisuuksia voidaan säädellä lämpötilan avulla. Veden pintajännitys, viskositeetti, tiheys ja polaarisuus pienenevät lämpötilan kasvaessa, ja alikriittisen veden aineominaisuudet muuttuvat lähemmäksi orgaanista liuotinta. Alikriittisen veden dielektrisyysvakion aleneminen johtuu pääasiassa lämpötilan vaikutuksesta ja vain vähän paineen vaikutuksesta. Alikriittistä vettä on käytetty liuottimena uutossa, mutta nyt myös alikriittinen kromatografia on kehittymässä oleva erotusmenetelmä. Työn kokeellisessa osassa kehitettiin kromatografinen laitteisto alikriittiselle vedelle, jolla tutkittiin sokerialkoholien ja sokerien kromatografista erotusta alikriittisen veden avulla. Lisäksi tutkittiin sokerialkoholien, sokereiden ja stationäärifaasien termistä kestävyyttä. Tutkittavina komponentteina olivat sorbitoli, mannitoli, ksylitoli, arabinoosi, mannoosi, ksyloosi, maltoosi ja ramnoosi. Stationäärifaaseina käytettiin makrohuokoista funktionalisoimatonta polystyreenidivinyylibentseenikopolymeeriä, sekä vahvoja ja heikkoja divinyylibentseenillä ristisilloitettuja kationinvaihtohartseja, jotka olivat joko Na+- tai Ca2+-ionimuodoissa. Veden lämpötilan nostaminen vaikuttaa sekä kromatografisen stationäärifaasin tilavuusmuutoksiin että näytekomponenttien ominaisuuksiin. Vahvoilla kationinvaihtimilla havaittiin termisten tilavuusmuutosten riippuvan ionimuodosta: Na+-muotoiset hartsit turpoavat ja Ca2+-muotoiset kutistuvat lämpötilan noustessa. Heikot kationinvaihtimet kutistuvat molemmissa ionimuodoissa, mutta Ca2+-muoto kutistuu Na+-muotoa voimakkaammin. Näytekomponenteista sokerialkoholien havaittiin kestävän paremmin korkeita lämpötiloja kuin sokerien. Sokerialkoholeista kestävimmäksi havaittiin ksylitoli ja sokereista ramnoosi. Tutkittavien komponenttien piikkien havaittiin kapenevan, häntimisen vähenevän, ja piikkien eluoituvan aikaisemmin riippuen käytettävästä stationäärifaasista. Ca2+-muotoisen vahvan kationinvaihtimen kompleksinmuodostuskyky heikkeni lämpötilan kasvaessa. Näytekomponenttien erotus ei kuitenkaan parantunut lämpötilan noustessa tutkituilla stationäärifaaseilla.

A study of electromagnetic shielding properties of Ni79Fe16Mo5/copper films

The plane wave electromagnetic interference (EMI) shielding properties of DC sputtered Ni79Fe16Mo5 and copper layers were studied according to ASTM D 4935-89 on frequency range of 50 MHz – 2.5 GHz and RF magnetic shielding effectiveness by shielded magnetic loop probes. Results show that Ni79Fe16Mo5 provides better RF magnetic shielding above the layer thickness of approximately 120 nm. Copper provides better plane wave shielding effectiveness. The effect of shield internal interfaces was studied by depositing thin multilayer structures with and without a dielectric spacer layer.

High voltage discharge for degradation of organic contaminants in water

The pulsed dielectric barrier discharge (PDBD) and pulsed corona discharge (PCD) were compared for their efficiency to degrade phenol in water solution. Results show that PCD has higher efficiency than PDBD to degrade phenol. When initial pH of water solution was elevated, phenol degradation in the PCD reactor was significantly enhanced, although no considerable effect was seen in the PDBD reactor. The PCD reactor was also able to degrade lignin significantly, both in synthetically prepared solution and in pulp and paper mill wastewater. Water temperature did not affect phenol degradation; however, lignin was better oxidized at lower temperature.

Maakaapelien kuntomittaukset

Kandidaatintyössä on luotu katsaus maakaapelirakenteisiin ja erilaisiin maakaapelien kuntomittausmenetelmiin, kuten osittaispurkausmittaus ja dielektrisen vasteen mittaaminen. Työssä on myös esitelty muutamat yleisimmät mittauslaitteistot ja sivuttu lyhyesti mittausten hyödyntämistä kunnossapidossa.

Yleismittarikortin prototyypin suunnittelu modulaariseen testauslaitteeseen

Tämä diplomityö on osa erään yrityksen sisäistä tuotekehitysprojektia. Projektin päämäärä oli kehittää ja tuoda markkinoille uusi modulaarinen testilaite. Markkinoille tuotava laite voi asiakkaan toivomuksesta pitää sisällään jännitelujuus-, eristysvastus- ja vuotovirtamittarin. Tämän lisäksi uuteen testilaitteeseen on mahdollista lisätä muita sisäisiä rele- ja mittalaitekortteja mm. yleismittarimoduulin. Diplomityössä perehdytään elektroniikan eri suureiden mittaamiseen, sekä syvennytään modulaarisen testilaitteen yleismittarikortin prototyypin suunnitteluun. Prototyypin tuli vastata tarkkuudeltaan ja nopeudeltaan markkinoiden johtavien mittalaitevalmistajien tarjoamia yleiskäyttöön tarkoitettuja järjestelmäyleismittareita. Työn lopputuloksena syntyi digitaaliyleismittarikortin prototyyppi. Käytännön syistä prototyyppikortin mittaustulokset ja tulosten käsittely on rajattu kokonaan pois tästä kirjallisesta dokumentista.

Design of Pulsed Electroacoustic Measurement System for Space Charge Characterisation

Pulsed electroacoustic (PEA) method is a commonly used non-destructive technique for investigating space charges. It has been developed since early 1980s. These days there is continuing interest for better understanding of the influence of space charge on the reliability of solid electrical insulation under high electric field. The PEA method is widely used for space charge profiling for its robust and relatively inexpensive features. The PEA technique relies on a voltage impulse used to temporarily disturb the space charge equilibrium in a dielectric. The acoustic wave is generated by charge movement in the sample and detected by means of a piezoelectric film. The spatial distribution of the space charge is contained within the detected signal. The principle of such a system is already well established, and several kinds of setups have been constructed for different measurement needs. This thesis presents the design of a PEA measurement system as a systems engineering project. The operating principle and some recent developments are summarised. The steps of electrical and mechanical design of the instrument are discussed. A common procedure for measuring space charges is explained and applied to verify the functionality of the system. The measurement system is provided as an additional basic research tool for the Corporate Research Centre of ABB (China) Ltd. It can be used to characterise flat samples with thickness of 0.2–0.5 mm under DC stress. The spatial resolution of the measurement is 20 μm.

Carbon Nanotubes as Material for Supercapacitor Electrodes

Electrochemical double-layer supercapacitors have an intermediate position between rechargeable batteries, which can store high amounts of energy, and dielectric capacitors, which have high output power. Supercapacitors are widely suggested to be used in automobiles (recuperation during braking, facilitate engine starting, electric stabilization of the system), industry (forklifts, elevators), hybrid off-road machinery and also in consumer electronics. Supercapacitor electrodes require highly porous material. Typically, activated carbon is used. Specific surface area of activated carbon is approximately 1000 m2 per gram. Carbon nanotubes represent one of prospective materials. According to numerous studies this material allows to improve the properties of supercapacitors. The task of this Master‘s Thesis was to test multiwalled carbon nanotubes and become confident with the testing methods.

Research and development of III-V semiconductor surfaces for improved device interfaces

This thesis is devoted to understanding and improving technologically important III-V compound semiconductor (e.g. GaAs, InAs, and InSb) surfaces and interfaces for devices. The surfaces and interfaces of crystalline III-V materials have a crucial role in the operation of field-effect-transistors (FET) and highefficiency solar-cells, for instance. However, the surfaces are also the most defective part of the semiconductor material and it is essential to decrease the amount of harmful surface or interface defects for the next-generation III-V semiconductor device applications. Any improvement in the crystal ordering at the semiconductor surface reduces the amount of defects and increases the material homogeneity. This is becoming more and more important when the semiconductor device structures decrease to atomic-scale dimensions. Toward that target, the effects of different adsorbates (i.e., Sn, In, and O) on the III-V surface structures and properties have been investigated in this work. Furthermore, novel thin-films have been synthesized, which show beneficial properties regarding the passivation of the reactive III-V surfaces. The work comprises ultra-high-vacuum (UHV) environment for the controlled fabrication of atomically ordered III-V(100) surfaces. The surface sensitive experimental methods [low energy electron diffraction (LEED), scanning tunneling microscopy/spectroscopy (STM/STS), and synchrotron radiation photoelectron spectroscopy (SRPES)] and computational density-functionaltheory (DFT) calculations are utilized for elucidating the atomic and electronic properties of the crucial III-V surfaces. The basic research results are also transferred to actual device tests by fabricating metal-oxide-semiconductor capacitors and utilizing the interface sensitive measurement techniques [capacitance voltage (CV) profiling, and photoluminescence (PL) spectroscopy] for the characterization. This part of the thesis includes the instrumentation of home-made UHV-compatible atomic-layer-deposition (ALD) reactor for growing good quality insulator layers. The results of this thesis elucidate the atomic structures of technologically promising Sn- and In-stabilized III-V compound semiconductor surfaces. It is shown that the Sn adsorbate induces an atomic structure with (1×2)/(1×4) surface symmetry which is characterized by Sn-group III dimers. Furthermore, the stability of peculiar ζa structure is demonstrated for the GaAs(100)-In surface. The beneficial effects of these surface structures regarding the crucial III-V oxide interface are demonstrated. Namely, it is found that it is possible to passivate the III-V surface by a careful atomic-scale engineering of the III-V surface prior to the gate-dielectric deposition. The thin (1×2)/(1×4)-Sn layer is found to catalyze the removal of harmful amorphous III-V oxides. Also, novel crystalline III-V-oxide structures are synthesized and it is shown that these structures improve the device characteristics. The finding of crystalline oxide structures is exploited by solving the atomic structure of InSb(100)(1×2) and elucidating the electronic structure of oxidized InSb(100) for the first time.

Pulsed corona discharge as an advanced oxidation process for degradation of organic

Advanced oxidation processes (AOPs) have been studied and developed to suffice the effective removal of refractory and toxic compounds in polluted water. The quality and cost of wastewater treatment need improvements, and electric discharge technology has a potential to make a significant difference compared to other established AOPs based on energy efficiency. The generation of active oxidant species such as ozone and hydroxyl radicals by high voltage discharge is a relatively new technology for water treatment. Gas-phase pulsed corona discharge (PCD), where a treated aqueous solution is dispersed between corona-producing electrodes free of the dielectric barriers, was developed as an alternative approach to the problem. The short living radicals and ozone formed in the gas phase and at the gas-liquid interface react with dissolved impurities. PCD equipment has a relatively simple configuration, and with the reactor in an enclosed compartment, it is insensitive towards gas humidity and does not need the gas transport. In this thesis, PCD was used to study and evaluate the energy efficiency for degrading various organic compounds, as well as the chemistry of the oxidation products formed. The experiments investigate the aqueous oxidation of phenol, humic substances, pharmaceutical compounds (paracetamol, ibuprofen, indomethacin, salicylic acids, -estradiol), as well as lignin degradation and transformation to aldehydes. The study aims to establish the influence of initial concentration of the target pollutant, the pulsed discharge parameters, gas phase composition and the pH on the oxidation kinetics and the efficiency. Analytical methods to measure the concentrations of the target compounds and their by-products include HPLC, spectrophotometry, TOC and capillary electrophoresis. The results of the research included in this summary are presented in the attached publications and manuscripts accepted for publication. Pulsed corona discharge proved to be highly effective in oxidizing each of the target compounds, surpassing the closest competitor, conventional ozonation. The increase in oxidation efficiencies for some compounds in oxygen media and at lower pulse repetition frequencies shows a significant role of ozone. The role of the ·OH radicals was established in the surface reactions. The main oxidation products, formation of nitrates, and the lignin transformation were quantified. A compound specific approach is suggested for optimization of the PCD parameters that have the most significant impact on the oxidation energy efficiency because of the different characteristics and responses of the target compound to the oxidants, as well as different admixtures that are present in the wastewater. Further studies in the method’s safety (nitration and nitrosation of organic compounds, nitrite and nitrate formation enhancement) are needed for promoting the method.

Novel technology for preparation of optically active chemicals

Asymmetric synthesis using modified heterogeneous catalysts has gained lots of interest in the production of optically pure chemicals, such as pharmaceuticals, nutraceuticals, fragrances and agrochemicals. Heterogeneous modified catalysts capable of inducing high enantioselectivities are preferred in industrial scale due to their superior separation and handling properties. The topic has been intensively investigated both in industry and academia. The enantioselective hydrogenation of ethyl benzoylformate (EBF) to (R)-ethyl mandelate over (-)-cinchonidine (CD)-modified Pt/Al2O3 catalyst in a laboratory-scale semi-batch reactor was studied as a function of modifier concentration, reaction temperature, stirring rate and catalyst particle size. The main product was always (R)-ethyl mandelate while small amounts of (S)-ethyl mandelate were obtained as by product. The kinetic results showed higher enantioselectivity and lower initial rates approaching asymptotically to a constant value as the amount of modifier was increased. Additionally, catalyst deactivation due to presence of impurities in the feed was prominent in some cases; therefore activated carbon was used as a cleaning agent of the raw material to remove impurities prior to catalyst addition. Detailed characterizations methods (SEM, EDX, TPR, BET, chemisorption, particle size distribution) of the catalysts were carried out. Solvent effects were also studied in the semi-batch reactor. Solvents with dielectric constant (e) between 2 and 25 were applied. The enantiomeric excess (ee) increased with an increase of the dielectric coefficient up to a maximum followed by a nonlinear decrease. A kinetic model was proposed for the enantioselectivity dependence on the dielectric constant based on the Kirkwood treatment. The non-linear dependence of ee on (e) successfully described the variation of ee in different solvents. Systematic kinetic experiments were carried out in the semi-batch reactor. Toluene was used as a solvent. Based on these results, a kinetic model based on the assumption of different number of sites was developed. Density functional theory calculations were applied to study the energetics of the EBF adsorption on pure Pt(1 1 1). The hydrogenation rate constants were determined along with the adsorption parameters by non-linear regression analysis. A comparison between the model and the experimental data revealed a very good correspondence. Transient experiments in a fixed-bed reactor were also carried out in this work. The results demonstrated that continuous enantioselective hydrogenation of EBF in hexane/2-propanol 90/10 (v/v) is possible and that continuous feeding of (-)-cinchonidine is needed to maintain a high steady-state enantioselectivity. The catalyst showed a good stability and high enantioselectivity was achieved in the fixed-bed reactor. Chromatographic separation of (R)- and (S)-ethyl mandelate originating from the continuous reactor was investigated. A commercial column filled with a chiral resin was chosen as a perspective preparative-scale adsorbent. Since the adsorption equilibrium isotherms were linear within the entire investigated range of concentrations, they were determined by pulse experiments for the isomers present in a post-reaction mixture. Breakthrough curves were measured and described successfully by the dispersive plug flow model with a linear driving force approximation. The focus of this research project was the development of a new integrated production concept of optically active chemicals by combining heterogeneous catalysis and chromatographic separation technology. The proposed work is fundamental research in advanced process technology aiming to improve efficiency and enable clean and environmentally benign production of enantiomeric pure chemicals.