Reaction Kinetics and Viscosity Modelling in the Fusion Syntheses of Ca- and Ca/Mg-resinates

Rosin is a natural product from pine forests and it is used as a raw material in resinate syntheses. Resinates are polyvalent metal salts of rosin acids and especially Ca- and Ca/Mg- resinates find wide application in the printing ink industry. In this thesis, analytical methods were applied to increase general knowledge of resinate chemistry and the reaction kinetics was studied in order to model the non linear solution viscosity increase during resinate syntheses by the fusion method. Solution viscosity in toluene is an important quality factor for resinates to be used in printing inks. The concept of critical resinate concentration, c crit, was introduced to define an abrupt change in viscosity dependence on resinate concentration in the solution. The concept was then used to explain the non-inear solution viscosity increase during resinate syntheses. A semi empirical model with two estimated parameters was derived for the viscosity increase on the basis of apparent reaction kinetics. The model was used to control the viscosity and to predict the total reaction time of the resinate process. The kinetic data from the complex reaction media was obtained by acid value titration and by FTIR spectroscopic analyses using a conventional calibration method to measure the resinate concentration and the concentration of free rosin acids. A multivariate calibration method was successfully applied to make partial least square (PLS) models for monitoring acid value and solution viscosity in both mid-infrared (MIR) and near infrared (NIR) regions during the syntheses. The calibration models can be used for on line resinate process monitoring. In kinetic studies, two main reaction steps were observed during the syntheses. First a fast irreversible resination reaction occurs at 235 °C and then a slow thermal decarboxylation of rosin acids starts to take place at 265 °C. Rosin oil is formed during the decarboxylation reaction step causing significant mass loss as the rosin oil evaporates from the system while the viscosity increases to the target level. The mass balance of the syntheses was determined based on the resinate concentration increase during the decarboxylation reaction step. A mechanistic study of the decarboxylation reaction was based on the observation that resinate molecules are partly solvated by rosin acids during the syntheses. Different decarboxylation mechanisms were proposed for the free and solvating rosin acids. The deduced kinetic model supported the analytical data of the syntheses in a wide resinate concentration region, over a wide range of viscosity values and at different reaction temperatures. In addition, the application of the kinetic model to the modified resinate syntheses gave a good fit. A novel synthesis method with the addition of decarboxylated rosin (i.e. rosin oil) to the reaction mixture was introduced. The conversion of rosin acid to resinate was increased to the level necessary to obtain the target viscosity for the product at 235 °C. Due to a lower reaction temperature than in traditional fusion synthesis at 265 °C, thermal decarboxylation is avoided. As a consequence, the mass yield of the resinate syntheses can be increased from ca. 70% to almost 100% by recycling the added rosin oil.

Estudi de viabilitat tecnològica de tags RFID sobre diferents substrats

En aquest projecte s’han dissenyat i simulat diferents models de tags RFID per a la banda UHF sobre diferents classes de substrats i tintes conductores amb l’objectiu d’estudiar la viabilitat de la tecnologia de Printed Electronics per a la seva d’implementació física. A partir de dues configuracions ja existents a la literatura, aquestes etiquetes RFID s’han modelat electromagnèticament mitjançant el software ADS i s’ha simulat la seva resposta freqüencial. En segon terme, a fi d’avaluar el seu rendiment, també s’ha representat el read range d’aquests tags RFID en funció d’aquestes tintes conductores i substrats. Posteriorment, s’han realitzat diferents proves de fabricació mitjançant un mètode basat en la serigrafia, així com d’obtenció experimental de la seva distància de lectura. Finalment, en base als resultats obtinguts s’ha pogut concloure que és viable realitzar tags RFID segons aquesta tècnica d’impressió, però a falta d’una verificació experimental únicament a nivell de simulació.

Medidas tipográficas: un recuento

Breve repaso al desarrollo de la concepción métrica en la tipografía en plomo, alternativa y complemento de la visión habitual en lo que conocemos como 'tipometría'. Se parte de una noción amplia de medida: el factor cuantitativo se dilata con la articulación de relaciones proporcionales e integra la dimensión cualitativa de los sistemas métricos tradicionales. La tipografía se considera bajo presupuestos similares: como sistema articulado de piezas materiales cuyas magnitudes contienen usos y valores específicos, más allá de su simple expresión numérica. Con tales premisas, se revisan fuentes documentales significativas del 'período de la imprenta manual'. Su examen, vinculado a los usos y costumbres de oficio, desvela la distinta aproximación métrica, que puede resumirse en tres fases evolutivas: hermética, intensiva, expansiva como recogen las referencias de los cuerpos tipográficos: adjetivas, sustantivas, numéricas. Se proporciona así un marco para apreciar el cambio de sentido en las medidas tipográficas hasta nuestros días.

Paperin pintaenergian vaikutus painovärin tarpeeseen

Työn tavoitteena oli selvittää pintaenergian vaikutus painovärin tarpeeseen IGT-laboratoriopainokoneella. Lisäksi selvitettiin onko karheudella vaikutusta kontaktikulmamittaukseen. Työ koostui kirjallisuusosasta ja kokeellisesta osasta. Kirjallisuusosassa tarkasteltiin aihepiiriä koskevia teorioita ja aiempia tutkimuksia. Kokeellisessa osassa valmistettiin laboratoriomittakaavassa pintaenergialtaan ja karheudeltaan erilaisia papereita. Pintaenergiaa muuteltiin kolmen erilaisen massaliiman ja kahden erilaisen pintaliiman avulla. Paperin karheutta säädettiin kalanteroinnilla. Papereista mitattiin pintaominaisuuksia, nesteen ja paperin välinen kontaktikulma, sekä suoritettiin painatuskokeita. Pintaenergia laskettiin kirjallisuudesta löytyneiden teorioiden perusteella ja näiden pintaenergian laskemismenetelmien käyttökelpoisuutta pintaenergian määrittämiseen selvitettiin. Lisäksi tutkittiin pintaenergian vaikutusta painovärin tarpeeseen. Tämä työ selvästi osoittaa, että yhden, kahden ja kolmen komponentin menetelmällä ja nesteitä vaihtelemalla saadaan erilaisia pintaenergian tuloksia. Pintaenergian määrittämiseen vaikuttaa myös kontaktikulmamittausten hankaluus ja kontaktikulman suuri vaihtelu, joka vaikuttaa koko mittaussarjan luotettavuustarkasteluun. Lisäksi paperin karheudella ja huokoisuudella oli merkitystä kontaktikulmamittaukseen.

Massan fraktioiden vaikutus paperin bulkin ja sileyden väliseen yhteyteen

Diplomityön tavoitteena oli selvittää paperin valmistuksessa käytettävien mekaanisten massojen eri kuitufraktioiden vaikutusta SC-paperin ominaisuuksiin. Aikakausipaperin vaatimuksena on hyvä paperin sileys, kiilto ja bulkki. Sileys ja kiilto on helppo saavuttaa kalanteroimalla, mutta tällöin menetetään paperin bulkkia. Tässä työssä keskitytäänkin etsimään keinoja paperin bulkin säästämiseksi fraktioinnin avulla. Työn kirjallisuusosassa käydään läpi teoriaa paperin valmistuksesta ja paperin ominaisuuksista. Työn kokeellisessa osassa on esitetty tehdyt tutkimukset laboratoriomenetelmin kalanterointiolosuhteiden ja massojen eri fraktioiden vaikutuksesta paperin ominaisuuksiin. Saadut tulokset olivat samantyyppisiä mitä edellisissä tutkimuksissa samasta aiheesta oli saatu. Saatujen tulosten mukaan paperin pitkäkuitufraktion osuutta kasvattamalla bulkki ja taivutusjäykkyys paranivat, mutta toisaalta sileys ja kiilto huononivat. Paperin hienoainefraktion osuutta kasvattamalla kaikki painatusominaisuudet paranivat kuten sileys, kiilto ja valonsirontakerroin, mutta samalla huononivat paperin bulkki ja taivutusjäykkyys.

Optimization of a heatset dryer

The objective of the thesis was to examine the possibilities in designing better performing nozzles for the heatset drying oven in Forest Pilot Center. To achieve the objective, two predesigned nozzle types along with the replicas of the current nozzles in the heatset drying oven were tested on a pilot-scale dryer. During the runnability trials, the pilot dryer was installed between the last printing unit and the drying oven. The two sets of predesigned nozzles were consecutively installed in the dryer. Four web tension values and four different impingement air velocities were used and the web behavior during the trial points was evaluated and recorded. The runnability in all trial conditions was adequate or even good. During the heat transfer trials, each nozzle type was tested on at least two different nozzle-to-surface distances and four different impingement air velocities. In a test situation, an aluminum plate fitted with thermocouples was set below a nozzle and the temperature measurement of each block was logged. From the measurements, a heat transfer coefficient profile for the nozzle was calculated. The performance of each nozzle type in tested conditions could now be rated and compared. The results verified that the predesigned simpler nozzles were better than the replicas. For runnability reasons, there were rows of inclined orifices on the leading and trailing edges of the current nozzles. They were believed to deteriorate the overall performance of the nozzle, and trials were conducted to test this hypothesis. The perpendicular orifices and inclined orifices of a replica nozzle were consecutively taped shut and the performance of the modified nozzles was measured as before, and then compared to the performance of the whole nozzle. It was found out, that after a certain nozzle-to-surface distance the jets from the two nozzles would collide, which deteriorates the heat transfer.

Percepció i coneixements dels estudiants d'infermeria sobre la violència en la parella

Les últimes dades de l'estudi europeu del 2014, sobre la violència de parella indiquen que gairebé 62 milions de dones europees, havien sofert actes de violència de gènere, entre els quals es destaca els relacionats amb la violència de parella (VP). Els maltractaments constitueixen un problema molt greu que genera al nostre país cada vegada més alarma social i més actuacions legals i professionals per fer-li front. El sistema de salut és, amb freqüència, el primer lloc al que les víctimes de violència domèstica acudeixen a la recerca d'assessorament i ajuda, sent aquest el motiu pel qual els professionals de la salut tenen un paper central per a la seva assistència. Aquests formen part implicada en el sistema de detecció, atenció i actuació. Per això, els plans d'estudi de Grau d'Infermeria recullen en el BOE la formació en VP des de l’àmbit universitari. L’objectiu del nostre estudi consisteix en la identificació de la percepció i dels coneixements en relació a la violència de parella dels estudiants del Grau d’Infermeria de la Universitat de Girona durant el curs acadèmic 2012-2013. Per a dur-lo a terme es va realitzar un anàlisi quantitatiu dels resultats a través de l’administració d’una enquesta sobre sis aspectes de la VP, l’enquesta incloïa el perfil demogràfic (sexe, edat i anys d'estudi) dels estudiants i les declaracions relatives a les seves percepcions i coneixements sobre la VP: causes d'abús; la identificació de les dones objecte de VP i del seus autors; creences de les infermeres; funcions perceptibles; i la preparació educativa. Els estudiants del Grau d’Infermeria mostren tenir un bon coneixement sobre les causes del abús en VP, així com una formació adequada. També cal destacar que un 54,42% dels alumnes enquestats es veuen capacitats per afrontar un cas de VP com a infermer/a. S’observa una millora de la formació educativa en el transcurs acadèmic. En 1r curs un 40,09% té una bona formació, aquest valor augmenta fins a un 56,58% a tercer curs, baixant lleugerament fins un 44,27% a 4rt curs. Els resultats obtinguts són semblats a estudis de mostres similars en estudiants d'infermeria de Memphis (EUA) i de la University of Southern Queensland (Austràlia) quant a coneixements i percepció sobre la VP. Encara que els resultats mostren un coneixement i una percepció sobre la VP adequada, destaquem que això no succeeix en gairebé un 40% dels enquestats. La introducció de matèries específiques sobre igualtat i sobre violència contra la dona en els plans d’estudis, pot esdevenir una mesura preventiva per revisar i corregir possibles mites i creences en VP. Per tant, és necessari millorar la formació del currículum en estudiants d'infermeria per la importància d'aquest greu problema de salut pública, donant major èmfasis en la satisfacció de les necessitats emocionals i en la comprensió dels diferents enfocaments en VP, especialment en mesures de prevenció i educació

Espacio público: universidad, censura y política. Un ensayo visual

Lisbon, October 27, 2014, Dr. Jose Luis Cardoso director of the Institute of Social Sciences (ICS) at the University of Lisbon, has suspended the publication of the number 212 of the prestigious journal Análise Social. The reason: the number contains a visual essay produced by Ricardo Campos that is qualified to use a 'strong language'. While the online edition of the magazine was available (not try to find it at the site of the ICS) the printed edition was in printing machines. Now, the hard copies will be destroyed.

The Impact of Aspen and Alder on the Quality of NHBK

The purpose of this work was to study the effect of aspen and alder on birch cooking and the quality of the pulp produced. Three different birch kraft pulps were studied. As a reference, pure aspen and alder were included. The laboratory trials were done at the UPM Research Centre in Lappeenranta, Finland. The materials used were birch, aspen and alder mill chips that were collected around the area of South-Carelia in Finland. The chips used in the study were pulped using a standard kraft process. The pulps including birch fibres were ECF-bleached at laboratory scale to a target brightness of 85 %. The bleached pulps were beaten at low consistency by a laboratory Voith Sulzer refiner and tested for optical and physical properties. The theoretical part is a study of hardwoods that takes into accounts the differences between birch, aspen and alder. Major sub-areas were fibre and paper-technical properties as well as chemical composition and their influence on the different properties. The pulp properties of birch, aspen and alder found in previous studies were reported. Russian hardwood forest resources were also investigated. The fundamentals of kraft pulping and bleaching were studied at the end of theoretical part. The major effect of replacing birch with aspen and alder was the deterioration (lowering) of tensile and tear strengths. In other words, addition of aspen and alder to a birch furnish reduced strength properties. The reinforcement ability of the tested pulps was the following: 100 % birch > 80 % birch, 20 % aspen > 70 % birch, 20 % aspen, 10 % alder. The second thing noted was that blending of birch together with aspen and alder give better smoothness, optical properties and also formation. It can be concluded, that replacement of birch with alder during cooking by more than 10 % can negatively affect on the paper-technical properties of birch pulp. Mixing pure birch and aspen pulps would be more beneficial when producing printing paper made from chemical pulp.

Desenvolvimento de processo de produção de conjuntos eletrodo-membrana-eletrodo para células a combustível baseadas no uso de membrana polimérica condutora de prótons (PEMFC) por impressão a tela

Proton exchange membrane fuel cell (PEMFC) requires membrane electrode assemblies (MEA) to generate electrical energy from hydrogen and oxygen. In this study a MEA production process by sieve printing and an ink composition were developed to produce catalyst layers of MEAs. The deposition of the exact catalyst content was possible on cathodes and anodes with only one print step. The optimal ink developed shown viscosity of 2.75 Pa s, density 1.27 g cm-3, total solid content of 33.76 % and tack of 92 U.T. The electrodes prepared in only one printing step showed higher performance than those prepared in several steps.

Desenvolvimento de tecnologia para confecção de eletrodos e conjuntos eletrodo-membrana-eletrodo (MEA) por impressão à tela para aplicação em módulos de potência de células PEMFC

Significant functions in the Proton Exchange Membrane Fuel Cells (PEMFCs) rely on Gas Diffusion Layers (GDLs), such as control the water balance in the membrane electrode assembly (MEA), allow suitable gas permeability and porosity, etc. Aware of the GDL importance in the cell performance and its great demand in scale-up projects, the fuel cell research group at Instituto de Pesquisas Energéticas e Nucleares (IPEN) has developed a Sieve Printing method (innovative in Brazil) as a strategic solution for producing GDL and electrodes used in high power PEMFC stacks. The method has shown to be adequate to fabricate low cost electrodes, GDLs of different dimensions and to produce any amount of MEAs for power stacks.

Measurement and Improvement of Wet Paper Web Strength

Various strength properties of paper are measured to tell how well it resists breaks in a paper machine or in printing presses. The most often measured properties are dry tensile strength and dry tear strength. However, in many situations where paper breaks, it is not dry. For example, in web breaks after the wet pressing the dry matter content can be around 45%. Thus, wet-web strength is often a more critical paper property than dry strength. Both wet and dry strength properties of the samples were measured with a L&W tensile tester. Originally this device was not designed for the measurement of the wet web tensile strength, thus a new procedure to handle the wet samples was developed. The method was tested with Pine Kraft (never dried). The effect of different strength additives on the wet-web and dry paper tensile strength was studied. The polymers used in this experiment were aqueous solution of a cationic polyamidoamine-epichlorohydrin resin (PAE), cationic hydrophilised polyisocyanate and cationic polyvinylamine (PVAm). From all three used chemicals only Cationic PAE considerably increased the wet web strength. However it was noticed that at constant solids content all chemicals decreased the wet web tensile strength. So, since all chemicals enhanced solid content it can be concluded that they work as drainage aids, not as wet web strength additives. From all chemicals only PVAm increased the dry strength and two other chemicals even decreased the strength. As chemicals were used in strong diluted forms and were injected into the pulp slurry, not on the surface of the papersheets, changes in samples densities did not happen. Also it has to be noted that all these chemicals are mainly used to improve the wet strength after the drying of the web.

Elintarvikekelpoisten painovärien vertailu offsetpainatuksessa

Tässä diplomityössä tutkittiin kolmen eri painovärivalmistajan elintarvikekelpoisia arkkioffsetpainovärisarjoja ja verrattiin niitä keskenään. Tavoitteena oli löytää optimaalinen elintarvikekartonkipakkausten painamiseen soveltuva arkkioffsetpainoväri. Työn kirjallisessa osassa selvitettiin yleisesti offsetpainatusprosessia, painovärien koostumusta ja elintarvikekelpoisten painovärien eroavaisuutta verrattuna perinteisiin offsetpainoväreihin. Kirjallisuusosassa tuotiin esille myös niitä tekijöitä, joilla elintarvikekelpoisuus määritellään. Näistä yksi tärkeä osa-alue on migraatio-ongelmat, joka on lainsäädännön kannalta ajankohtainen. Kokeellista osaa varten koepainovärejä painettiin taivekartongille arkkioffsetpainokoneella. Painetuista arkeista tehtiin mittauksia, joissa käytettiin densitometrisia, kolorimetrisia, kromatografisia ja aistinvaraisia menetelmiä. Näillä pyrittiin tuomaan esille eroavaisuuksia tutkittavana olleiden painovärien välille. Koeajojen ja mittausten perusteella analysoitiin painatuksen laatua, painettavuutta, painovärien elintarvikekelpoisuutta ja kestävyyttä. Työn tulosten perusteella ei voida suoraan osoittaa, että jokin painovärisarja olisi toimivampi kuin toinen. Yksi johtopäätös olikin, että painovärien koostumusta ja painatusprosessia on mahdollista modifioida monella tavalla, jolloin voidaan parantaa joitakin painovärin ominaisuuksia. Yleisesti kokeet osoittivat, että perinteinen aistinvarainen tapa testata painovärin elintarvikekelpoisuutta on hyvin subjektiivinen ja antaa arveluttavia tuloksia. Koetuloksista oli kuitenkin havaittavissa, että uuden sukupolven vähemmän migraatiota aiheuttavat painovärit ovat elintarvikekelpoisempia kuin aikaisempien kehitysasteiden painovärisarjat.

Agile CRM System Implementation Project

The application of information technology (IT) in customer relationship management (CRM) is growing rapidly as many companies implement CRM systems to support their numerous customer facing activities. However, failure rates of CRM projects remain notably high as they deliver scant solutions and poor user acceptance. As a consequence, it is justified to study previously researched CRM success factors and apply them to CRM system implementation. The aim of this master’s thesis was to get acquainted with relevant academic theories, frameworks and practices concerning CRM and agile development, and use them to generate a modified CRM project strategy to support the successful execution of the case company’s, Process Vision Oy, CRM implementation project. The empirical CRM system implementation project was conducted simultaneously with writing this thesis. Its theoretical findings could be transferred into practice through active participation in the CRM system development and deployment work. The project’s main goal was to produce and take into use a functioning CRM system. The goal was met, since at the time of printing this thesis the first system release was successfully published to its users at Process Vision’s marketing and sales departments. The key success elements in the CRM project were cyclic, iterative system development, customer oriented approach, user inclusion and flexible project management. Implying agile development practices ensured being able to quickly respond to changes arising during the progress of the CRM project. Throughout modelling of the core sales process formed a strong basis, on which the CRM system’s operational and analytical functionalities were built. End users were included in the initial specification of system requirements and they provided feedback on the system’s usage. To conclude, the chosen theoretical CRM roadmaps and agile development practices proved as beneficial in the successful planning and execution of the agile CRM system implementation project at Process Vision.

Painotuotteen hinnoittelu kypsillä markkinoilla

Tämä tutkimus tarkastelee hinnoittelua graafisen teollisuuden pk-sektorin kirjapainoissa. Alalla vallitseva markkinatilanne on kiristynyt siirryttäessä kysyntä-/teknologiaelinkaaren kasvujaksolta kypsään vaiheeseen. Tutkimus pyrkii antamaan vastauksen hinnoittelun tarvitsemaan toimintaan tarkastelemalla hinnoittelun ”ongelmien järjestelmää”. Tutkimus on toiminta-analyyttisen metodologian mukaisena tutkimuksena toteutettu case-tutkimus, jossa empirian tutkimusmetodeina ovat kvalitatiiviset puolistruktuuriset teemahaastattelut ja kvantitatiiviset tilastolliset tarkastelut toimialan kehityksestä. Tutkimustuloksina todetaan alalla vallinneen pitkän voimakkaan kannattavuuden jakson muokanneen case-yrityksen hinnoitteluperiaatteita, jotka vastaavat huonosti muuttuneeseen markkinatilanteeseen. Tutkimuksessa esitetään pk-yrittäjien rationaalisuuden ero talousteorioiden edellyttämästä instrumentaalisesta rationaalisuudesta.