Antireflection coatings from analogy between electron scattering and spin precession

We use the analogy between scattering of a wave from a potential, and the precession of a spin-half particle in a magnetic field, to gain insight into the design of an antireflection coating for electrons in a semiconductor superlattice. It is shown that the classic recipes derived for optics are generally not applicable due to the different dispersion law for electrons. Using the stability conditions we show that a Poisson distribution of impedance steps is a better approximation than is a Gaussian distribution. Examples are given of filters with average transmissivity exceeding 95% over an allowed band.

Photocatalytic Activity of Nanostructured Anatase Coatings Obtained by Cold Gas Spray

This article describes a photocatalytic nanostructured anatase coating deposited by cold gas spray (CGS)supported on titanium sub-oxide (TiO22x) coatings obtained by atmospheric plasma spray (APS) onto stainless steel cylinders. The photocatalytic coating was homogeneous and preserved the composition and nanostructure of the starting powder. The inner titanium sub-oxide coating favored the deposition of anatase particles in the solid state. Agglomerated nano-TiO2 particles fragmented when impacting onto the hard surface of the APS TiO22x bond coat. The rough surface provided by APS provided an ideal scenario for entrapping the nanostructured particles, which may be adhered onto the bond coat due to chemical bonding; a possible bonding mechanism is described. Photocatalytic experiments showed that CGS nano-TiO2 coating was active for photodegrading phenol and formic acid under aqueous conditions. The results were similar to the performance obtained by competitor technologies and materials such as dip-coating P25 photocatalysts. Disparity in the final performance of the photoactive materials may have been caused by differences in grain size and the crystalline composition of titanium dioxide.

Cyclosporine A kinetics in brain cell cultures and its potential of crossing the blood-brain barrier.

There is an increasing need to develop improved systems for predicting the safety of xenobiotics. However, to move beyond hazard identification the available concentration of the test compounds needs to be incorporated. In this study cyclosporine A (CsA) was used as a model compound to assess the kinetic profiles in two rodent brain cell cultures after single and repeated exposures. CsA induced-cyclophilin B (Cyp-B) secretion was also determined as CsA-specific pharmacodynamic endpoint. Since CsA is a potent p-glycoprotein substrate, the ability of this compound to cross the blood-brain barrier (BBB) was also investigated using an in vitro bovine model with repeated exposures up to 14days. Finally, CsA uptake mechanisms were studied using a parallel artificial membrane assay (PAMPA) in combination with a Caco-2 model. Kinetic results indicate a low intracellular CsA uptake, with no marked bioaccumulation or biotransformation. In addition, only low CsA amounts crossed the BBB. PAMPA and Caco-2 experiments revealed that CsA is mostly trapped to lipophilic compartments and exits the cell apically via active transport. Thus, although CsA is unlikely to enter the brain at cytotoxic concentrations, it may cause alterations in electrical activity and is likely to increase the CNS concentration of other compounds by occupying the BBBs extrusion capacity. Such an integrated testing system, incorporating BBB, brain culture models and kinetics could be applied for assessing neurotoxicity potential of compounds.

Barrier-protective effects of activated protein C in human alveolar epithelial cells

Acute lung injury (ALI) is a clinical manifestation of respiratory failure, caused by lung inflammation and the disruption of the alveolar-capillary barrier. Preservation of the physical integrity of the alveolar epithelial monolayer is of critical importance to prevent alveolar edema. Barrier integrity depends largely on the balance between physical forces on cell-cell and cell-matrix contacts, and this balance might be affected by alterations in the coagulation cascade in patients with ALI. We aimed to study the effects of activated protein C (APC) on mechanical tension and barrier integrity in human alveolar epithelial cells (A549) exposed to thrombin. Cells were pretreated for 3 h with APC (50 mg/ml) or vehicle (control). Subsequently, thrombin (50 nM) or medium was added to the cell culture. APC significantly reduced thrombin-induced cell monolayer permeability, cell stiffening, and cell contraction, measured by electrical impedance, optical magnetic twisting cytometry, and traction microscopy, respectively, suggesting a barrier-protective response. The dynamics of the barrier integrity was also assessed by western blotting and immunofluorescence analysis of the tight junction ZO-1. Thrombin resulted in more elongated ZO-1 aggregates at cell-cell interface areas and induced an increase in ZO-1 membrane protein content. APC attenuated the length of these ZO-1 aggregates and reduced the ZO-1 membrane protein levels induced by thrombin. In conclusion, pretreatment with APC reduced the disruption of barrier integrity induced by thrombin, thus contributing to alveolar epithelial barrier protection.

Coatings on Composites

Polymer based composite materials coated with thin layers of wear resistant materials have been proposed as replacements for steel components for certain applications with the advantage of reduced mass. Magnetron sputtered coatings can be successfully deposited on composite materials. Nevertheless there are number of issues which must be addressed such as limited temperature, which the composite can withstand because of the epoxy binder which is used, the adhesion of the coating to the composite and the limited mechanical support, the hard coating can obtain from the relatively soft epoxy. We have investigated the deposition of chromium nitride, titanium carbide and titanium doped DLC coatings on carbon fibre reinforced composites and various polymers. The adhesion of the coatings has been studied by the pull-off adhesion tester. In general, the failure mechanism has been noticed to be due to the cohesive failure for a wide range of conditions. The wear behavior of the coatings has been noticed to be complicated. Wear tests on coated composites have shown that where the reinforcing fibres are near the surface, the composite samples do not perform well due to breakage of the fibres from the polymer matrix. A fibre free surface has been noticed to improve the wear resistance.

Loss of intestinal epithelial barrier function in Salmonella Enteritidis infection

Intestinal infection with Salmonella enterica serotype Enteritidis, a food-borne infection spread to humans especially through contaminated eggs and egg-products as well as undercooked contaminated fresh meat, is the most common cause of intestinal inflammation in the European Union. Enteritis caused by Salmonella Enteritidis is characterized by fever, diarrhoea and abdominal pain. The disruption of the intestinal epithelial barrier function contributes to diarrhoea and is responsible for the perpetuation of the inflammatory process. In this sense, oxidative stress and the proinflammatory cytokines TNF-α, IFN-γ and IL-1β are described to induce the disorganization of the tight junctions (TJ), the most apical epithelial intercellular junctions and responsible for the paracellular permeability. The interest of this chapter relies not only in the investigation dealing with the mechanisms of TJ regulation but also in the contribution to the development of new tools for the prevention of epithelial barrier disruption in enteritis caused by Salmonella Enteritidis.

Effects of the epitaxial layer thickness on the noise properties of Schottky barrier diodes

An analytical theory to describe the combined effects of the epitaxial layer thickness and the ohmic contact on the noise properties of Schottky barrier diodes is presented. The theory, which provides information on both the local and the global noise properties, takes into account the finite size of the epitaxial layer and the effects of the back ohmic contact, and applies to the whole range of applied bias. It is shown that by scaling down the epitaxial layer thickness, the current regime in which the noise temperature displays a shot-noise-like behavior increases at the cost of reducing the current range in which the thermal-noise-like behavior dominates. This improvement in noise temperature is limited by the effects of the ohmic contact, which appear for large currents. The theory is formulated on general trends, allowing its application to the noise analysis of other semiconductor devices operating under strongly inhomogeneous distributions of the electric field and charge concentrations.

Effects of the epitaxial layer thickness on the noise properties of Schottky barrier diodes

An analytical theory to describe the combined effects of the epitaxial layer thickness and the ohmic contact on the noise properties of Schottky barrier diodes is presented. The theory, which provides information on both the local and the global noise properties, takes into account the finite size of the epitaxial layer and the effects of the back ohmic contact, and applies to the whole range of applied bias. It is shown that by scaling down the epitaxial layer thickness, the current regime in which the noise temperature displays a shot-noise-like behavior increases at the cost of reducing the current range in which the thermal-noise-like behavior dominates. This improvement in noise temperature is limited by the effects of the ohmic contact, which appear for large currents. The theory is formulated on general trends, allowing its application to the noise analysis of other semiconductor devices operating under strongly inhomogeneous distributions of the electric field and charge concentrations.

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

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

Influence of topography and surface chemistry on the wetting properties of TiO2-based ceramic coatings

Vätning av fasta ytor är ett viktigt fenomen i såväl naturen som i en lång rad av industriella tillämpningar. Det är allmänt känt att vätningen av en fast yta styrs av ytans kemi samt struktur. Målsättningen med avhandlingen var att studera hur kemisk heterogenitet och ytråhet på nanometernivå påverkar vätningsegenskaperna hos en fast yta. Ytorna som studerades var titandioxid-baserade kerama ytor som framställdes med hjälp av en sol-gel process. Vätningstudierna utfördes genom kontaktvinkelmätningar, vilket innebär att man mäter vinkeln som vätska/luft-gränsskiktet hos en vätskedroppe bildar mot en fast yta. Ytråheten hos materialen studerades främst genom atomkraftsmikroskopi (AFM). I AFM detekteras ytans struktur av en mycket skarp nål som skannar ytan. Resultaten i avhandlingen kunde framgångsrikt modelleras med existerande teorier för vätning av heterogena ytor.

Enhancing performance of paper coatings by tailor-made plastic pigments

The paper industry is constantly looking for new ideas for improving paper products while competition and raw material prices are increasing. Many paper products are pigment coated. Coating layer is the top layer of paper, thus by modifying coating pigment also the paper itself can be altered and value added to the final product. In this thesis, synthesis of new plastic and hybrid pigments and their performance in paper and paperboard coating is reported. Two types of plastic pigments were studied: core-shell latexes and solid beads of maleimide copolymers. Core-shell latexes with partially crosslinked hydrophilic polymer core of poly(n-butyl acrylate-co-methacrylic acid) and a hard hydrophobic polystyrene shell were prepared to improve the optical properties of coated paper. In addition, the effect of different crosslinkers was analyzed and the best overall performance was achieved by the use of ethylene glycol dimethacrylate (EGDMA). Furthermore, the possibility to modify core-shell latex was investigated by introducing a new polymerizable optical brightening agent, 1-[(4-vinylphenoxy)methyl]-4-(2-henylethylenyl)benzene which gave promising results. The prepared core-shell latex pigments performed smoothly also in pilot coating and printing trials. The results demonstrated that by optimizing polymer composition, the optical and surface properties of coated paper can be significantly enhanced. The optimal reaction conditions were established for thermal imidization of poly(styrene-co-maleimide) (SMI) and poly(octadecene-co-maleimide) (OMI) from respective maleic anhydride copolymer precursors and ammonia in a solvent free process. The obtained aqueous dispersions of nanoparticle copolymers exhibited glass transition temperatures (Tg) between 140-170ºC and particle sizes from 50-230 nm. Furthermore, the maleimide copolymers were evaluated in paperboard coating as additional pigments. The maleimide copolymer nanoparticles were partly imbedded into the porous coating structure and therefore the full potential of optical property enhancement for paperboard was not achieved by this method. The possibility to modify maleimide copolymers was also studied. Modifications were carried out via N-substitution by replacing part of the ammonia in the imidization reaction with amines, such as triacetonediamine (TAD), aspartic acid (ASP) and fluorinated amines (2,2,2- trifluoroethylamine, TFEA and 2,2,3,3,4,4,4-heptafluorobuthylamine, HFBA). The obtained functional nanoparticles varied in size between 50-217 nm and their Tg from 150-180ºC. During the coating process the produced plastic pigments exhibited good runnability. No significant improvements were achieved in light stability with TAD modified copolymers whereas nanoparticles modified with aspartic acid and those containing fluorinated groups showed the desired changes in surface properties of the coated paperboard. Finally, reports on preliminary studies with organic-inorganic hybrids are presented. The hybrids prepared by an in situ polymerization reaction consisted of 30 wt% poly(styrene- co-maleimide) (SMI) and high levels of 70 wt% inorganic components of kaolin and/or alumina trihydrate. Scanning Electron Microscopy (SEM) images and characterization by Fourier Transform Infrared Spcetroscopy (FTIR) and X-Ray Diffraction (XRD) revealed that the hybrids had conventional composite structure and inorganic components were covered with precipitated SMI nanoparticles attached to the surface via hydrogen bonding. In paper coating, the hybrids had a beneficial effect on increasing gloss levels.

Rasvankestävät paperit ja kartongit

Rasvankestävyydellä tarkoitetaan sitä, että materiaali hylkii tai kestää rasvaa tietyn ajan läpäisemättä sen pintaa. Rasvankestäviä papereita ja kartonkeja löytyy kaikkialta. Erilaiset ruuanvalmistuspaperit, kuten esimerkiksi leivinpaperi ja voipaperi, ovat rasvankestäviä. Myös pakkauksissa käytetään paljon rasvankestäviä papereita ja kartonkeja. Rasvankestäviltä tuotteilta vaaditaan erilaisia ominaisuuksia riippuen niiden käyttötarkoituksesta. Pakkausmateriaaleilta vaaditaan esimerkiksi lujuutta ja kestävyyttä fyysistä rasitusta, valoa, hajuja ja mikrobeja vastaan. Ruuanvalmistusmateriaaleilta vaaditaan puolestaan lujuutta ja kestävyyttä lämpöä, kosteutta ja fyysistä rasitusta vastaan. Rasvankestäviltä papereilta vaaditaan rasvankestävyyden lisäksi hyvää vetolujuutta, märkälujuutta ja hyviä optisia ominaisuuksia. Neliömassan tulee asettua 20─80 g/m2 välille ja metallipitoisuudet eivät saa olla liian korkeat. Myös tuotteiden kierrätettävyys on nostanut asemaansa viimeaikoina. Tuotteen tuotannon ja itse tuotteen ympäristöystävällisyys ovat todella arvostettuja kuluttajan, tuottajan, Suomen, EU:n ja koko maailman näkökulmista. Jotta tuotteesta saadaan rasvankestävää, vaaditaan siltä erilaisia barrier-ominaisuuksia. Rasvankestävällä paperilla vaaditaan hyviä barrier-ominaisuuksia esimerkiksi rasvan, ilman, veden, vesihöyryn sekä hapen läpäisevyyksissä. Rasvankestäviä papereita ja kartonkeja voidaan valmistaa kemiallisilla ja mekaanisilla tavoilla. Happokäsittely ja fluorokemikaalien lisääminen ovat kemiallisia tapoja, kun taas sellun jauhaminen pitkään matalassa lämpötilassa on mekaaninen tapa valmistaa rasvankestävää paperia. Näiden tapojen lisäksi rasvankestäviä papereita voidaan tehdä erilaisten pinnoitusten avulla. Erilaiset muovit ovat yleisemmin käytettyjä pinnoitemateriaaleja. Esimerkiksi PE- ja PET-päällysteet ovat käytettyjä rasvankestävissä tuotteissa. Viime aikoina on kehitetty paljon erilaisia biomateriaaleja, joista voidaan tehdä rasvankestävä pinnoite. Lipideistä, hydrokolloideista ja erilaisista komposiiteista voidaan luoda uusien tekniikoiden avulla rasvankestäviä pinnoitteita. Rasvankestävyydestä voidaan saada jonkinlainen käsitys WVTR-asteen, Cobb-arvon ja kontaktikulman mittausten avulla. Rasvankestävyyttä voidaan myös mitata erilaisten standarditestien avulla. TAPPI:lla, ISO:lla ja ASTM:llä on useita erilaisia standardeja. Lähes kaikissa rasvankestävyysstandardeissa tuloksen saaminen perustuu visuaaliseen havaintoon, mikä aiheuttaa välillä hankaluuksia tulosten luotettavuuteen, koska tuloksen määrittää ihmissilmä, ja kaikilla testin tekijöillä on erilainen silmä, joka aistii eri tavalla.

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.

Surface characterization of chemically modified fiber, wood and paper

Inorganic-organic sol-gel hybrid coatings can be used for improving and modifying properties of wood-based materials. By selecting a proper precursor, wood can be made water repellent, decay-, moisture- or UV-resistant. However, to control the barrier properties of sol-gel coatings on wood substrates against moisture uptake and weathering, an understanding of the surface morphology and chemistry of the deposited sol-gel coatings on wood substrates is needed. Mechanical pulp is used in production of wood-containing printing papers. The physical and chemical fiber surface characteristics, as created in the chosen mechanical pulp manufacturing process, play a key role in controlling the properties of the end-use product. A detailed understanding of how process parameters influence fiber surfaces can help improving cost-effectiveness of pulp and paper production. The current work focuses on physico-chemical characterization of modified wood-based materials with surface sensitive analytical tools. The overall objectives were, through advanced microscopy and chemical analysis techniques, (i) to collect versatile information about the surface structures of Norway spruce thermomechanical pulp fiber walls and understand how they are influenced by the selected chemical treatments, and (ii) to clarify the effect of various sol-gel coatings on surface structural and chemical properties of wood-based substrates. A special emphasis was on understanding the effect of sol-gel coatings on the water repellency of modified wood and paper surfaces. In the first part of the work, effects of chemical treatment on micro- and nano-scale surface structure of 1st stage TMP latewood fibers from Norway spruce were investigated. The chemicals applied were buffered sodium oxalate and hydrochloric acid. The outer and the inner fiber wall layers of the untreated and chemically treated fibers were separately analyzed by light microscopy, atomic force microscopy and field-emission scanning electron microscopy. The selected characterization methods enabled the demonstration of the effect of different treatments on the fiber surface structure, both visually and quantitatively. The outer fiber wall areas appeared as intact bands surrounding the fiber and they were clearly rougher than areas of exposed inner fiber wall. The roughness of the outer fiber wall areas increased most in the sodium oxalate treatment. The results indicated formation of more surface pores on the exposed inner fiber wall areas than on the corresponding outer fiber wall areas as a result of the chemical treatments. The hydrochloric acid treatment seemed to increase the surface porosity of the inner wall areas. In the second part of the work, three silane-based sol-gel hybrid coatings were selected in order to improve moisture resistance of wood and paper substrates. The coatings differed from each other in terms of having different alkyl (CH3–, CH3-(CH2)7–) and fluorocarbon (CF3–) chains attached to the trialkoxysilane sol-gel precursor. The sol-gel coatings were deposited by a wet coating method, i.e. spraying or spreading by brush. The effect of solgel coatings on surface structural and chemical properties of wood-based substrates was studied by using advanced surface analyzing tools: atomic force microscopy, X-ray photoelectron spectroscopy and time-of-flight secondary ion spectroscopy. The results show that the applied sol-gel coatings, deposited as thin films or particulate coatings, have different effects on surface characteristics of wood and wood-based materials. The coating which has a long hydrocarbon chain (CH3-(CH2)7–) attached to the silane backbone (octyltriethoxysilane) produced the highest hydrophobicity for wood and wood-based materials.

Dual light barrier method for six degrees of freedom tool center point calibration of an industrial robot

Tool center point calibration is a known problem in industrial robotics. The major focus of academic research is to enhance the accuracy and repeatability of next generation robots. However, operators of currently available robots are working within the limits of the robot´s repeatability and require calibration methods suitable for these basic applications. This study was conducted in association with Stresstech Oy, which provides solutions for manufacturing quality control. Their sensor, based on the Barkhausen noise effect, requires accurate positioning. The accuracy requirement admits a tool center point calibration problem if measurements are executed with an industrial robot. Multiple possibilities are available in the market for automatic tool center point calibration. Manufacturers provide customized calibrators to most robot types and tools. With the handmade sensors and multiple robot types that Stresstech uses, this would require great deal of labor. This thesis introduces a calibration method that is suitable for all robots which have two digital input ports free. It functions with the traditional method of using a light barrier to detect the tool in the robot coordinate system. However, this method utilizes two parallel light barriers to simultaneously measure and detect the center axis of the tool. Rotations about two axes are defined with the center axis. The last rotation about the Z-axis is calculated for tools that have different width of X- and Y-axes. The results indicate that this method is suitable for calibrating the geometric tool center point of a Barkhausen noise sensor. In the repeatability tests, a standard deviation inside robot repeatability was acquired. The Barkhausen noise signal was also evaluated after recalibration and the results indicate correct calibration. However, future studies should be conducted using a more accurate manipulator, since the method employs the robot itself as a measuring device.