Investigation ofsolid - state cooler based on electrocaloric effect

Electrocaloric cooling based on ability of material to change temperature by applying an electric field under adiabatic conditions is relatively new and challenging direction of ferroelectrics research. In this work we report about analytical, simulation and experimental data for BaSrTiO3 thin film and bulk ceramic samples. Detailed discussion of a theoretical base of the electrocaloric effect is included. Demonstrated experimental and computational results exemplify rational approach to a problem of solid-state cooler construction.

Väkevän urealiuoksen puhdistaminen kalvotekniikalla

Kirjallisuusosassa käsiteltiin nanosuodatus-, käänteisosmoosi- ja elektrodialyysitekniikoita liuosten puhdistuksessa. Nanosuodatuksella ja käänteisosmoosilla voidaan liuottimesta erottaa pienen moolimassan omaavia liuenneita aineita ohuen kalvon avulla. Nanosuodatuksessa ja käänteisosmoosissa ajavana voimana on paine, jonka tulee ylittää liuoksen osmoottinen paine. Elektrodialyysissä ajavana voimana toimii sähköpotentiaaliero. Tekniikka käyttää hyväkseen ionien tai molekyylien kykyä johtaa sähköä. Elektrodialyysillä voidaan liuoksesta erottaa toisistaan varauksettomat ja varaukselliset komponentit sähköä johtavan membraanin avulla. Kokeellisessa osassa väkevää ureavesiliuosta suodatettiin nanosuodatus- ja käänteisosmoosikalvoilla tutkien paineen, lämpötilan ja konsentroitumisen vaikutusta vuohonja retentioon. Tarkoituksena oli saada urea tuotteena permeaattiin ja epäpuhtaudet erottumaan retentaattiin. Permeaattien epäpuhtauksien pitoisuuksia verrattiin tuotteen spesifikaation raja-arvoihin. Suodatukset tehtiin Lappeenrannan teknillisen yliopiston tiloissa DSS Labstak M20 suotimella. Työssä käytettiin NF1-, NF2-, NF270-, NF-, NF90-, Desal-5 DK-, OPMN-P 70- ja TFC ULP-kalvoja. Nanosuodatuskalvot NF2- ja NF270 antoivat parhaan vuon ja erotuskyvyn suhteen puhdistettaessa urealiuosta. Paineen noustessa kalvojen retentiot paranivat. Lämpötilan noustessa vuo parani, joskin täytyy huomioida urean kiihtyvä hajoaminen lähestyttäessä 40 °C astetta. Kalvojen kestävyyttä ureasuodatuksissa ei voitu näiden kokeiden avulla varmentaa.

Cryo-electron microscopy of vitreous sections of native biological cells and tissues : methodology and applications

Résumé L'eau est souvent considérée comme une substance ordinaire puisque elle est très commune dans la nature. En fait elle est la plus remarquable de toutes les substances. Sans l'eau la vie sur la terre n'existerait pas. L'eau représente le composant majeur de la cellule vivante, formant typiquement 70 à 95% de la masse cellulaire et elle fournit un environnement à d'innombrables organismes puisque elle couvre 75% de la surface de terre. L'eau est une molécule simple faite de deux atomes d'hydrogène et un atome d'oxygène. Sa petite taille semble en contradiction avec la subtilité de ses propriétés physiques et chimiques. Parmi celles-là, le fait que, au point triple, l'eau liquide est plus dense que la glace est particulièrement remarquable. Malgré son importance particulière dans les sciences de la vie, l'eau est systématiquement éliminée des spécimens biologiques examinés par la microscopie électronique. La raison en est que le haut vide du microscope électronique exige que le spécimen biologique soit solide. Pendant 50 ans la science de la microscopie électronique a adressé ce problème résultant en ce moment en des nombreuses techniques de préparation dont l'usage est courrant. Typiquement ces techniques consistent à fixer l'échantillon (chimiquement ou par congélation), remplacer son contenu d'eau par un plastique doux qui est transformé à un bloc rigide par polymérisation. Le bloc du spécimen est coupé en sections minces (d’environ 50 nm) avec un ultramicrotome à température ambiante. En général, ces techniques introduisent plusieurs artefacts, principalement dû à l'enlèvement d'eau. Afin d'éviter ces artefacts, le spécimen peut être congelé, coupé et observé à basse température. Cependant, l'eau liquide cristallise lors de la congélation, résultant en une importante détérioration. Idéalement, l'eau liquide est solidifiée dans un état vitreux. La vitrification consiste à refroidir l'eau si rapidement que les cristaux de glace n'ont pas de temps de se former. Une percée a eu lieu quand la vitrification d'eau pure a été découverte expérimentalement. Cette découverte a ouvert la voie à la cryo-microscopie des suspensions biologiques en film mince vitrifié. Nous avons travaillé pour étendre la technique aux spécimens épais. Pour ce faire les échantillons biologiques doivent être vitrifiés, cryo-coupées en sections vitreuse et observées dans une cryo-microscope électronique. Cette technique, appelée la cryo- microscopie électronique des sections vitrifiées (CEMOVIS), est maintenant considérée comme étant la meilleure façon de conserver l'ultrastructure de tissus et cellules biologiques dans un état très proche de l'état natif. Récemment, cette technique est devenue une méthode pratique fournissant des résultats excellents. Elle a cependant, des limitations importantes, la plus importante d'entre elles est certainement dû aux artefacts de la coupe. Ces artefacts sont la conséquence de la nature du matériel vitreux et le fait que les sections vitreuses ne peuvent pas flotter sur un liquide comme c'est le cas pour les sections en plastique coupées à température ambiante. Le but de ce travail a été d'améliorer notre compréhension du processus de la coupe et des artefacts de la coupe. Nous avons ainsi trouvé des conditions optimales pour minimiser ou empêcher ces artefacts. Un modèle amélioré du processus de coupe et une redéfinitions des artefacts de coupe sont proposés. Les résultats obtenus sous ces conditions sont présentés et comparés aux résultats obtenus avec les méthodes conventionnelles. Abstract Water is often considered to be an ordinary substance since it is transparent, odourless, tasteless and it is very common in nature. As a matter of fact it can be argued that it is the most remarkable of all substances. Without water life on Earth would not exist. Water is the major component of cells, typically forming 70 to 95% of cellular mass and it provides an environment for innumerable organisms to live in, since it covers 75% of Earth surface. Water is a simple molecule made of two hydrogen atoms and one oxygen atom, H2O. The small size of the molecule stands in contrast with its unique physical and chemical properties. Among those the fact that, at the triple point, liquid water is denser than ice is especially remarkable. Despite its special importance in life science, water is systematically removed from biological specimens investigated by electron microscopy. This is because the high vacuum of the electron microscope requires that the biological specimen is observed in dry conditions. For 50 years the science of electron microscopy has addressed this problem resulting in numerous preparation techniques, presently in routine use. Typically these techniques consist in fixing the sample (chemically or by freezing), replacing its water by plastic which is transformed into rigid block by polymerisation. The block is then cut into thin sections (c. 50 nm) with an ultra-microtome at room temperature. Usually, these techniques introduce several artefacts, most of them due to water removal. In order to avoid these artefacts, the specimen can be frozen, cut and observed at low temperature. However, liquid water crystallizes into ice upon freezing, thus causing severe damage. Ideally, liquid water is solidified into a vitreous state. Vitrification consists in solidifying water so rapidly that ice crystals have no time to form. A breakthrough took place when vitrification of pure water was discovered. Since this discovery, the thin film vitrification method is used with success for the observation of biological suspensions of. small particles. Our work was to extend the method to bulk biological samples that have to be vitrified, cryosectioned into vitreous sections and observed in cryo-electron microscope. This technique is called cryo-electron microscopy of vitreous sections (CEMOVIS). It is now believed to be the best way to preserve the ultrastructure of biological tissues and cells very close to the native state for electron microscopic observation. Since recently, CEMOVIS has become a practical method achieving excellent results. It has, however, some sever limitations, the most important of them certainly being due to cutting artefacts. They are the consequence of the nature of vitreous material and the fact that vitreous sections cannot be floated on a liquid as is the case for plastic sections cut at room temperature. The aim of the present work has been to improve our understanding of the cutting process and of cutting artefacts, thus finding optimal conditions to minimise or prevent these artefacts. An improved model of the cutting process and redefinitions of cutting artefacts are proposed. Results obtained with CEMOVIS under these conditions are presented and compared with results obtained with conventional methods.

In situ spectroellipsometric study of the nucleation and growth of amorphous silicon

A detailed in situ spectroellipsometric analysis of the nucleation and growth of hydrogenated amorphous silicon (a:Si:H) is presented. Photoelectronic quality a‐Si:H films are deposited by plasma‐enhanced chemical vapor deposition on smooth metal (NiCr alloy) and crystalline silicon (c‐Si) substrates. The deposition of a‐Si:H is analyzed from the first monolayer up to a final thickness of 1.2 μm. In order to perform an improved analysis, real time ellipsometric trajectories are recorded, using fixed preparation conditions, at various photon energies ranging from 2.2 to 3.6 eV. The advantage of using such a spectroscopic experimental procedure is underlined. New insights into the nucleation and growth mechanisms of a‐Si:H are obtained. The nucleation mechanism on metal and c‐Si substrates is very accurately described assuming a columnar microstructural development during the early stage of the growth. Then, as a consequence of the incomplete coalescence of the initial nuclei, a surface roughness at the 10-15 Å scale is identified during the further growth of a‐Si:H on both substrates. The bulk a‐Si:H grows homogeneously beneath the surface roughness. Finally, an increase of the surface roughness is evidenced during the long term growth of a‐Si:H. However, the nature of the substrate influenced the film growth. In particular, the film thickness involved in the nucleation‐coalescence phase is found lower in the case of c‐Si (67±8 Å) as compared to NiCr (118±22 Å). Likewise films deposited on c‐Si present a smaller surface roughness even if thick samples are considered (>1 μm). More generally, the present study illustrates the capability of in situ spectroellipsometry to precisely analyze fundamental processes in thin‐film growth, but also to monitor the preparation of complex structures on a few monolayers scale.

Optoelectronic studies in nanocrystalline silicon Schottky diodes obtained by Hot-Wire Chemical Vapour Deposition

The very usual columnar growth of nanocrystalline silicon leads to electronic transport anisotropies. Whereas electrical measurements with coplanar electrodes only provide information about the electronic transport parallel to the substrate, it is the transverse transport which determines the collection efficiency in thin film solar cells. Hence, Schottky diodes on transparent electrodes were obtained by hot-wire CVD in order to perform external quantum efficiency and surface photovoltage studies in sandwich configuration. These measurements allowed to calculate a transverse collection length, which must correlate with the photovoltaic performance of thin film solar cells. Furthermore, the density of charge trapped at localized states in the bandgap was estimated from the voltage dependence of the depletion capacitance of these rectifying contacts.

Top-gate microcrystalline silicon TFTs processed at low temperature (<200ºC)

N-type as well P-type top-gate microcrystalline silicon thin film transistors (TFTs) are fabricated on glass substrates at a maximum temperature of 200 °C. The active layer is an undoped μc-Si film, 200 nm thick, deposited by Hot-Wire Chemical Vapor. The drain and source regions are highly phosphorus (N-type TFTs) or boron (P-type TFTs)-doped μc-films deposited by HW-CVD. The gate insulator is a silicon dioxide film deposited by RF sputtering. Al-SiO 2-N type c-Si structures using this insulator present low flat-band voltage,-0.2 V, and low density of states at the interface D it=6.4×10 10 eV -1 cm -2. High field effect mobility, 25 cm 2/V s for electrons and 1.1 cm 2/V s for holes, is obtained. These values are very high, particularly the hole mobility that was never reached previously.

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.

Photoelectric Measurements and Modeling of Bacteriorhodopsin

Recent technology has provided us with new information about the internal structures and properties of biomolecules. This has lead to the design of applications based on underlying biological processes. Applications proposed for biomolecules are, for example, the future computers and different types of sensors. One potential biomolecule to be incorporated in the applications is bacteriorhodopsin. Bacteriorhodopsin is a light-sensitive biomolecule, which works in a similar way as the light sensitive cells of the human eye. Bacteriorhodopsin reacts to light by undergoing a complicated series of chemical and thermal transitions. During these transitions, a proton translocation occurs inside the molecule. It is possible to measure the photovoltage caused by the proton translocations when a vast number of molecules is immobilized in a thin film. Also the changes in the light absorption of the film can be measured. This work aimed to develop the electronics needed for the voltage measurements of the bacteriorhodopsin-based optoelectronic sensors. The development of the electronics aimed to get more accurate information about the structure and functionality of these sensors. The sensors used in this work contain a thick film of bacteriorhodopsin immobilized in polyvinylalcohol. This film is placed between two transparent electrodes. The result of this work is an instrumentation amplifier which can be placed in a small space very close to the sensor. By using this amplifier, the original photovoltage can be measured in more detail. The response measured using this amplifier revealed two different components, which could not be distinguished earlier. Another result of this work is the model for the photoelectric response in dry polymer films.

Fractionation of wood hydrolysate by ultrafiltration membranes at high temperature

Ultrafiltration (UF) is already used in pulp and paper industry and its demand is growing because of the required reduction of raw water intake and the separation of useful compounds from process waters. In the pulp and paper industry membranes might be exposed to extreme conditions and, therefore, it is important that the membrane can withstand them. In this study, extractives, hemicelluloses and lignin type compounds were separated from wood hydrolysate in order to be able to utilise the hemicelluloses in the production of biofuel. The performance of different polymeric membranes at different temperatures was studied. Samples were analysed for total organic compounds (TOC), lignin compounds (UV absorption at 280 nm) and sugar. Turbidity, conductivity and pH were also measured. The degree of fouling of the membranes was monitored by measuring the pure water flux before and comparing it with the pure water flux after the filtration of hydrolysate. According to the results, the retention of turbidity was observed to be higher at lower temperature compared to when the filtrations were operated at high temperature (70 °C). Permeate flux increased with elevated process temperature. There was no detrimental effect of temperature on most of the membranes used. Microdyn-Nadir regenerated cellulose membranes (RC) and GE-Osmonics thin film membranes seemed to be applicable in the chosen process conditions. The Polyethersulphone (NF-PES-10 and UH004P) and polysulphone (MPS-36) membranes used were highly fouled, but they showed high retentions for different compounds.

Introdução às técnicas de reflexão especular e de reflexão-absorção no infravermelho: (2) reflexão-absorção

This paper is the second part of an article aimed to present theoretical basis as well as some applications of two infrared reflection techniques: specular reflection and reflection-absorption. It is emphasyzed how much spectral simulation can aid spectral analysis. The usefulness of reflection-absorption spectroscopy as a thin film caracterization technique is stressed. Optical effects such as LO-TO splittings and their observation as Berreman effect are also addressed.

Oxochloroalkoxide of the Cerium (IV) and Titanium (IV) as oxides precursor

The Cerium (IV) and Titanium (IV) oxides mixture (CeO2-3TiO2) was prepared by thermal treatment of the oxochloroisopropoxide of Cerium (IV) and Titanium (IV). The chemical route utilizing the Cerium (III) chloride alcoholic complex and Titanium (IV) isopropoxide is presented. The compound Ce5Ti15Cl16O30 (iOPr)4(OH-Et)15 was characterized by elemental analysis, FTIR and TG/DTG. The X-ray diffraction patterns of the oxides resulting from the thermal decomposition of the precursor at 1000 °C for 36 h indicated the formation of cubic cerianite (a = 5.417Å) and tetragonal rutile (a = 4.592Å) and (c = 2.962 Å), with apparent crystallite sizes around 38 and 55nm, respectively.

Filmes de titânio-silício preparados por "spin" e "dip-coating"

The conditions for the preparation of luminescent materials, consisting of Eu3+ ions entrapped in a titanium matrix, in the forma of a thin film, using the sol-gel process, are described. The films were obtained from sols prepared with TEOS and TEOT, in the presence of acetylacetone as the hidrolysis-retarding agent, using the dip-coating and spin-coating techniques. The influence of these techniques on the films based on titanium and silicon are presented. The Eu3+ was used as a luminescent probe. The films have been characterized by luminescence, reflection and transmittance. The thickness of the films could be related to the preparation procedure. Transparent thin films have been prepared by dip-coating technique.

Filmes delgados luminescentes obtidos a partir de hidroxicarbonatos de ítrio ativados por európio ou térbio

These films were obtained by dip coating. Parameters like dislocation velocity; number of deposits, suspension concentration, and number of deposits followed or not by heat treatment between each deposit and calcination temperature were evaluated for establishing the best homogeneity. The obtained films were characterized in terms of their morphology, optical quality and photoluminescence by scanning electron microscopy (SEM), UV-vis absorption spectrophotometry and luminescence spectroscopy, respectively. The morphologic and luminescent characteristics showed dip coating as good laboratory technique for development of thin films for optical applications.

Estabilização de solo contaminado com zinco usando zeólitas sintetizadas a partir de cinzas de carvão

The effect of synthetic zeolites on stabilizing Zn-contaminated soil using 0.01 mol L-1 CaCl2 leaching solution in batch experiments was investigated. The zeolites were synthesized from coal ash by hydrothermal treatment with alkaline solution. The additive enhanced the sorption capacity of the soil and reduced leaching. Zinc leaching was reduced by more than 80% using a minimum of 10% additive. The higher cation exchange capacity of the zeolite/soil mixtures and higher pH were responsible for stabilizing Zn in soil. The poly(2-aminobenzenesulfonic acid)-coated mercury thin-film electrode was used for the determination of zinc.

Labile copper and zinc fractions under different salinity conditions in a shipyard area in the patos lagoon estuary, south of Brazil

Copper and zinc are common elements in paint residues and can be toxic to estuarine organisms. This study aims to determine the labile dissolved and labile particulate fractions (LPFs) of copper and zinc in the estuarine waters of a shipyard in southern Brazil under different salinity levels and in different seasons. The labile dissolved fraction was determined using the diffusive gradient in thin-film (DGT) technique. The variations in DGT-Cu (0.22-1.05 µg L-1), DGT-Zn (0.54-18.39 µg L-1), LPF-Cu (1.22-3.77 µg g-1), and LPF-Zn (4.29-19.12 µg g-1) concentration were related to changes in their physico-chemical parameters and as a result of boat maintenance activities.