Tailored Jeffamine molecular tools for ordering mesoporous Silica

Herein, we report the formation of organized mesoporous silica materials prepared from a novel nonionic gemini surfactant, myristoyl-end capped Jeffamine, synthesized from a polyoxyalkyleneamine (ED900). The behavior of the modified Jeffamine in water was first investigated. A direct micellar phase (L1) and a hexagonal (H1) liquid crystal were found. The structure of the micelles was investigated from the SAXS and the analysis by Generalized Indirect Fourier Transformation (GIFT), which show that the particles are globular of coreshell type. The myristoyl chains, located at the ends of the amphiphile molecule are assembled to form the core of the micelles and, as a consequence, the molecules are folded over on themselves. Mesoporous materials were then synthesized from the self-assembly mechanism. The recovered materials were characterized by SAXS measurements, nitrogen adsorptiondesorption analysis, transmission and scanning electron microscopy. The results clearly evidence that by modifying the synthesis parameters, such as the surfactant/silica precursor molar ratio and the hydrothermal conditions, one can control the size and the nanostructuring of the resulting material. It was observed that, the lower the temperature of the hydrothermal treatment, the better the mesopore ordering.

Phase behavior and rheological analysis of reverse liquid crystals and W/I2, W/H2 gel emulsions using an amphiphilic block copolymer.

This article reports the phase behavior determi- nation of a system forming reverse liquid crystals and the formation of novel disperse systems in the two-phase region. The studied system is formed by water, cyclohexane, and Pluronic L-121, an amphiphilic block copolymer considered of special interest due to its aggregation and structural proper- ties. This system forms reverse cubic (I2) and reverse hexagonal (H2) phases at high polymer concentrations. These reverse phases are of particular interest since in the two-phase region, stable high internal phase reverse emulsions can be formed. The characterization of the I2 and H2 phases and of the derived gel emulsions was performed with small-angle X-ray scattering (SAXS) and rheometry, and the influence of temperature and water content was studied. TheH2 phase experimented a thermal transition to an I2 phase when temperature was increased, which presented an Fd3m structure. All samples showed a strong shear thinning behavior from low shear rates. The elasticmodulus (G0) in the I2 phase was around 1 order of magnitude higher than in theH2 phase. G0 was predominantly higher than the viscousmodulus (G00). In the gel emulsions,G0 was nearly frequency-independent, indicating their gel type nature. Contrarily to water-in-oil (W/O) normal emulsions, in W/I2 and W/H2 gel emulsions, G0, the complex viscosity (|η*|), and the yield stress (τ0) decreased with increasing water content, since the highly viscous microstructure of the con- tinuous phase was responsible for the high viscosity and elastic behavior of the emulsions, instead of the volumefraction of dispersed phase and droplet size. A rheological analysis, in which the cooperative flow theory, the soft glass rheology model, and the slip plane model were analyzed and compared, was performed to obtain one single model that could describe the non-Maxwellian behavior of both reverse phases and highly concentrated emulsions and to characterize their microstructure with the rheological properties.

Síntese de copolímeros em bloco com propriedades líquido cristalinas

The principal techniques for the synthesis of liquid crystalline block copolymers are reviewed. The syntheses are done by living/controlled free radical chain polymerization. The copolymers display an amorphous continuous phase and a discontinuous liquid crystalline phase (LC). The presence of oxypropylenic segments disturbs the range of mesophase transitions at lower temperatures. This behavior is not observed when styrenic segments are employed and suggests that the liquid crystalline behavior can be modified in block copolymers to show mesophases at higher and lower temperatures according to the flexibility of the chain segment that is present.

Desenvolvimento de sistemas líquido-cristalinos empregando silicone fluido de co-polímero glicol e poliéter funcional siloxano

For the construction of the phase diagrams, the method of the aqueous titration was used. There were prepared 5 ternary diagrams, varying the surfactant and the oil phase. The liquid-crystalline phases were identified by polarized light microscopy. The formulations prepared with silicon glycol copolymer, polyether functional siloxane (PFS) and water (S1) and with diisopropyl adipate, PFS and water (S4) presented liquid-crystalline phases with lamellar arrangement. Moreover, after 15 days in hot oven (37 ºC), the formulations presented hexagonal arrangement, evidencing the influence of the temperature in the organization of the system.

Argilas como catalisadores verdes na esterificação do colesterol: caracterização espectroscópica e identificação de polimorfos por métodos de análise térmica. Uma proposta laboratorial interdisciplinar para o 1º ciclo universitário

A laboratory experiment that enables the professor to introduce the problematic of sustainable development in pharmaceutical chemistry to undergraduate students is proposed, using a simple synthetic procedure. Cholesteryl acetate is prepared by the esterification of cholesterol using Montmorillonite K10 as heterogeneous catalyst. Cholesterol and cholesteryl acetate are characterized by spectroscopic (¹H RMN, 13C RMN, FTIR) and thermal analysis techniques. The thermal methods are used to introduce the concepts of polymorphism and the nature of mesophases.

Crescimento de cristais de rubi e safira pelo método do fluxo

This work reports the growth of corundum crystals by the flux method. The main objective was the evaluation of versatility, effectiveness and real possibilities of the flux method to the synthesis and doping of monocrystals with impurities of particular interest. In this work the chosen impurities were i) Cr and ii) Fe and Ti, aiming the synthesis of rubies and sapphires, respectively. The crystals were grown by heating a mixture of Al2O3:Cr or Al2O3:Fe:Ti and flux (MoO3). The maximum crystal size obtained was 1.0 mm, all transparent, presenting well developed faces, bipiramidal hexagonal shape, and showing a typical red (ruby) and/or light blue (sapphire) color. EDX and XPD experiments were performed in order to characterize some of the synthesized crystals. All crystallized specimens presented the α-alumina atomic structure.

Synthesis of indium tin oxide nanoparticles by a nonhydrolytic sol-gel method

Indium tin oxide nanoparticles were synthesized in two different sizes by a nonhydrolytic sol-gel method. These powders were then transformed into ITO via an intermediate metastable state at between 300 and 600 ºC. The presence of characteristic O-In-O and O-Sn-O bands at 480 and 670 cm-1 confirmed the formation of ITO. The X-ray diffraction patterns indicated the preferential formation of metastable hexagonal phase ITO (corundum type) as opposed to cubic phase ITO when the reflux time was less than 3 h and the heat treatment temperature was below 600 ºC. Particle morphology and crystal size were examined by scanning electron microscopy.

Caracterización de cristales líquidos por microscopía óptica en sistemas surfactante polietoxilado-alcano-agua

The phase behavior of an alcohol polyethoxylated surfactant with decane and dodecane oil phase varying the water proportion from 5 to 90% to determine compositions in which the formation of liquid crystals and microemulsions ocurred was investigated. Pseudoternary phase diagrams were built to represent the regions of liquid crystals, biphases and microemulsions. Polarized light optical microscopy was used for the analysis and characterization of the separate phases. The micrographs obtained showed characteristics of hexagonal and lamellar phases of liquid crystal, isotropic phases, microemulsions and vesicles. This study is important to propose hypothesis regarding the factors determining the formation and stability of phases composed by surfactant/oil/water systems.

Morphological analysis of the corneal endothelium in eyes of dogs using specular microscopy

Both healthy eyes of 10 six-year-old male and female mongrel dogs were studied. With a contact specular microscope the corneal endothelium was examined. Endothelial cells were analyzed in the central and peripheral cornea. Morphological analysis with regard to polymegathism and pleomorphism was performed. Three images of each region with at least 100 cells were obtained. The analysis showed that polygonal cells formed a mosaic-like pattern uniform in size and shape. The predominant number of cells was hexagonal. The polymegathism index was 0.22. The study demonstrates that the morphology of the normal corneal endothelial cells of dogs is similar to that found in the human cornea.

Estrutura morfológica do fígado de tambaqui Colossoma macropomum (Cuvier, 1818)

Este trabalho teve como objetivo descrever macro e microscopicamente o fígado do Tambaqui Colossoma macropomum, Teleósteo de água doce da Família Characidae, de grande interesse econômico da bacia Amazônica. Foram utilizados seis (6) exemplares jovens com idade entre seis meses e um ano, oriundos da Chácara Esteio, Alta Floresta, MT, que desenvolve principalmente a prática da piscicultura. O órgão foi fotodocumentado in situ e descrito macroscopicamente, em seguida procedeu-se a retirada de fragmentos deste, que foram processados pelas técnicas histológicas rotineiras para inclusão em parafina e coloração de HE. O fígado localizou-se ventral à bexiga natatória e craniodorsalmente ao estômago, apresentou coloração amarronzada a vermelho, constituído por três lobos hepáticos, o lobo lateral direito, o lobo lateral esquerdo e o lobo ventral. Microscopicamente, o parênquima era constituído por hepatócitos com formato que variou do arredondado irregular hexagonal ao redondo com núcleo grande e central, arranjados em cordões lineares limitados por sinusóides que irradiam para veias centrais, e com ausência de lóbulos hepáticos. As veias centrais estavam distribuídas pelo parênquima, enquanto que o espaço porta, na maioria das vezes, era constituído apenas por uma veia hepática e o ducto biliar, em outros locais foi observado, uma artéria e um ducto. Não foi observada a formação de tríades portais. Foram frequentemente observados melano macrófagos centrais dispersos pelo parênquima. O estudo morfofuncional do Aparelho Digestório de peixes da bacia Amazônica, se faz pertinente com vistas ao conhecimento do aproveitamento de ganho de peso e produção em alta escala para consumo humano e preservação da espécie, além da importância de estarem sendo utilizados como bioindicadores atualmente.

”Du sköna sång, vårt bästa arv” - kanonisering av en sångskatt ur ett hermeneutiskt perspektiv

Songs have the power to get through to people. When lyrics are combined with a tune, the result is an entity where the first few notes of a melody can evoke emotions of recognition and belonging. A song treasury consists of such songs that are part of a canonized song tradition. The process where certain songs become part of an established song treasury is long, and many other aspects than the tune itself influence the forming of a song treasury. By examining the characteristics of a song tradition, the history of an ethnic group can be illuminated. In this study, music, pedagogy, and the sociocultural context are merged into a whole where a common song tradition, the song treasury, is in focus. The main aim of this study is to deepen the understanding of a song treasury, its development and contents. This understanding is accomplished by analyzing the musical and lyrical characteristics of 60 songs, which have been sung in schools, homes, and communities, thereby becoming popular among the Swedish-speaking Finns during the 20th century. The songs have been chosen by combining three song lists, of which two lists are closely related to school curricula. The third song list is a result of a survey on favourite songs, according to the situation around year 2000. The songs are examined in their notated versions, a number of song books and text books (n = 29) forming the empirical material. In this study, a hermeneutical approach is applied, content analysis being the method. The analysis is based on three perspectives: the sociocultural perspective, the music-pedagogical perspective, and the musico-analytical perspective. Within each perspective, two aspects are studied. This results in a hexagonal model which forms the structure of the study as a whole. The first two perspectives form the background; a historical context where nation, education, home country, and homestead are regarded as highly important. A common song repertoire is considered to be an effective means of building collective identity within ethnic groups, the common language and the cultural heritage being used as rhetorical arguments. During the early 1900s, choir festivals become an educational platform where conceptions of a common belonging are developed and strengthened through religious, patriotic, and poetical expressions. National school curricula in singing and music have similar characteristics, cultural heritage and values education being in focus. The song lyrics often describe nature and emotions, and they also appear to be personal and situated in a given time and place. Patriotic expressions and songs about music are also fairly common. The songs generally express positive attitudes, which are intensified by major tonality, rich and varied melodies with stable rhythms, and a strong tonal base. The analyzed details of the studied aspects are merged into a thick description, which results in an interpretation pattern with three dimensions: a song treasury can be considered an expression of collective identity, cultural heritage, and values education.

M-käsittelyn vaikutus lastuamalla valmistettavan tuotteen valmistuskustannuksiin

Paremmin lastuttavia M-käsiteltyjä teräksiä on käytetty yrityksissä jo yli 20 vuoden ajan. Ominaisuuksiensa ansiosta M-teräksillä on pystytty pienentämään koneistuskustannuksia ja parantamaan kilpailukykyä. Viime vuosien aikana lastuavat terät ja työstökoneet ovat kuitenkin kehittyneet ja ero M-terästen ja tavanomaisten terästen välillä on voinut kaventua. Tämän diplomityön tavoitteena oli tutkia, saavutetaanko M-teräksen käytöllä taloudellisia etuja nykyaikaisissa konepajaolosuhteissa. Tutkimuksessa vertailtiin M-käsitellyn ja tavanomaisen 42CrMo4 – teräksen koneistusta. Valmistuskokeissa tarkasteltiin terien kulumista, lastun muotoa ja pinnanlaatua. Koekappaleena toimi olakkeellinen kuusiomutteri M64 kierteellä. Tuotteita valmistettiin yli 500 kappaletta ja materiaalia poistettiin noin 2000 kg. Koetulosten perusteella tuotteille laskettiin koneistuskustannukset kuvitteellisessa yrityksessä. Ero materiaalien välillä oli suurin työvaiheissa, joissa lastuaminen oli jatkuvaa. Sisä- ja ulkosorvauksessa M-käsiteltyä terästä lastunneiden terien kestoikä oli noin kaksinkertainen ja kierteen sorvauksessa noin nelinkertainen tavalliseen teräkseen verrattuna. Hakkaavassa työstössä terien kestoikä oli molemmilla materiaaleilla sama. Työssä suoritettujen kokeiden ja kustannuslaskelmien perusteella, käyttämällä M-käsiteltyä terästä voidaan pienentää valmistuskustannuksia. Materiaalien välinen ero korostuu, kun hakkaavaa työstöä on vähän, sarjat ovat suuria ja tuotanto on miehittämätöntä.

Model for subchannel friction factors and flow redistribution in wire-wrapped rod bundles

The fuel element of LMFBR consists of a bundle of rods wrapped with an helical wire as spacer, surrounded by an hexagonal duct. In the present work, a semi-empirical model is developed to calculate bundle average and subchannel based friction factors and flow redistribution. The obtained results were compared to experimental data and they were considered satisfactory for wide range of geometrical parameters.

Application and development of numerical methods for the modelling of innovative gas cooled fission reactors

Innovative gas cooled reactors, such as the pebble bed reactor (PBR) and the gas cooled fast reactor (GFR) offer higher efficiency and new application areas for nuclear energy. Numerical methods were applied and developed to analyse the specific features of these reactor types with fully three dimensional calculation models. In the first part of this thesis, discrete element method (DEM) was used for a physically realistic modelling of the packing of fuel pebbles in PBR geometries and methods were developed for utilising the DEM results in subsequent reactor physics and thermal-hydraulics calculations. In the second part, the flow and heat transfer for a single gas cooled fuel rod of a GFR were investigated with computational fluid dynamics (CFD) methods. An in-house DEM implementation was validated and used for packing simulations, in which the effect of several parameters on the resulting average packing density was investigated. The restitution coefficient was found out to have the most significant effect. The results can be utilised in further work to obtain a pebble bed with a specific packing density. The packing structures of selected pebble beds were also analysed in detail and local variations in the packing density were observed, which should be taken into account especially in the reactor core thermal-hydraulic analyses. Two open source DEM codes were used to produce stochastic pebble bed configurations to add realism and improve the accuracy of criticality calculations performed with the Monte Carlo reactor physics code Serpent. Russian ASTRA criticality experiments were calculated. Pebble beds corresponding to the experimental specifications within measurement uncertainties were produced in DEM simulations and successfully exported into the subsequent reactor physics analysis. With the developed approach, two typical issues in Monte Carlo reactor physics calculations of pebble bed geometries were avoided. A novel method was developed and implemented as a MATLAB code to calculate porosities in the cells of a CFD calculation mesh constructed over a pebble bed obtained from DEM simulations. The code was further developed to distribute power and temperature data accurately between discrete based reactor physics and continuum based thermal-hydraulics models to enable coupled reactor core calculations. The developed method was also found useful for analysing sphere packings in general. CFD calculations were performed to investigate the pressure losses and heat transfer in three dimensional air cooled smooth and rib roughened rod geometries, housed inside a hexagonal flow channel representing a sub-channel of a single fuel rod of a GFR. The CFD geometry represented the test section of the L-STAR experimental facility at Karlsruhe Institute of Technology and the calculation results were compared to the corresponding experimental results. Knowledge was gained of the adequacy of various turbulence models and of the modelling requirements and issues related to the specific application. The obtained pressure loss results were in a relatively good agreement with the experimental data. Heat transfer in the smooth rod geometry was somewhat under predicted, which can partly be explained by unaccounted heat losses and uncertainties. In the rib roughened geometry heat transfer was severely under predicted by the used realisable k − epsilon turbulence model. An additional calculation with a v2 − f turbulence model showed significant improvement in the heat transfer results, which is most likely due to the better performance of the model in separated flow problems. Further investigations are suggested before using CFD to make conclusions of the heat transfer performance of rib roughened GFR fuel rod geometries. It is suggested that the viewpoints of numerical modelling are included in the planning of experiments to ease the challenging model construction and simulations and to avoid introducing additional sources of uncertainties. To facilitate the use of advanced calculation approaches, multi-physical aspects in experiments should also be considered and documented in a reasonable detail.

Transformation of carbon dioxide to diethyl carbonate over ceria and ceria-supported catalysts

Carbon dioxide is regarded, nowadays, as a primary anthropogenic greenhouse gas leading to global warming. Hence, chemical fixation of CO2 has attracted much attention as a possible way to manufacture useful chemicals. One of the most interesting approaches of CO2 transformations is the synthesis of organic carbonates. Since conventional production technologies of these compounds involve poisonous phosgene and carbon monoxide, there is a need to develop novel synthetic methods that would better match the principles of "Green Chemistry" towards protection of the environment and human health. Over the years, synthesis of dimethyl carbonate was under intensive investigation in the academia and industry. Therefore, this study was entirely directed towards equally important homologue of carbonic esters family namely diethyl carbonate (DEC). Novel synthesis method of DEC starting from ethanol and CO2 over heterogeneous catalysts based on ceria (CeO2) was studied in the batch reactor. However, the plausible drawback of the reaction is thermodynamic limitations. The calculated values revealed that the reaction is exothermic (ΔrHØ298K = ─ 16.6 J/ ) and does not occur spontaneously at rooms temperature (ΔrGØ 298K = 35.85 kJ/mol). Moreover, co-produced water easily shifts the reaction equilibrium towards reactants excluding achievement of high yields of the carbonate. Therefore, in-situ dehydration has been applied using butylene oxide as a chemical water trap. A 9-fold enhancement in the amount of DEC was observed upon introduction of butylene oxide to the reaction media in comparison to the synthetic method without any water removal. This result confirms that reaction equilibrium was shifted in favour of the desired product and thermodynamic boundaries of the reaction were suppressed by using butylene oxide as a water scavenger. In order to obtain insight into the reaction network, the kinetic experiments were performed over commercial cerium oxide. On the basis of the selectivity/conversion profile it could be concluded that the one-pot synthesis of diethyl carbonate from ethanol, CO2 and butylene oxide occurs via a consecutive route involving cyclic carbonate as an intermediate. Since commercial cerium oxide suffers from the deactivation problems already after first reaction cycle, in-house CeO2 was prepared applying room temperature precipitation technique. Variation of the synthesis parameters such as synthesis time, calcination temperature and pH of the reaction solution turned to have considerable influence on the physico-chemical and catalytic properties of CeO2. The increase of the synthesis time resulted in high specific surface area of cerium oxide and catalyst prepared within 50 h exhibited the highest amount of basic sites on its surface. Furthermore, synthesis under pH 11 yielded cerium oxide with the highest specific surface area, 139 m2/g, among all prepared catalysts. Moreover, CeO2─pH11 catalyst demonstrated the best catalytic activity and 2 mmol of DEC was produced at 180 oC and 9 MPa of the final reaction pressure. In addition, ceria-supported onto high specific surface area silicas MCM-41, SBA-15 and silica gel were synthesized and tested for the first time as catalysts in the synthesis of DEC. Deposition of cerium oxide on MCM-41 and SiO2 supports resulted in a substantial increase of the alkalinity of the carrier materials. Hexagonal SBA-15 modified with 20 wt % of ceria exhibited the second highest basicity in the series of supported catalysts. Evaluation of the catalytic activity of ceria-supported catalysts showed that reaction carried out over 20 wt % CeO2-SBA-15 generated the highest amount of DEC.