Kontrollierte Fällung von amorphem Calciumcarbonat durch homogene Carbonatfreisetzung

In der Vergangenheit haben Untersuchung an biologischen und Modell-Systemen gezeigt, dass amorphes Calciumcarbonat als instabiles Zwischenprodukt bei der Bildung kristalliner Strukturen aus CaCO3 auftritt. Über dessen Rolle im Fällungsprozess von CaCO3 ist nicht viel bekannt und es wird davon ausgegangen, dass es als CaCO3-Speicher für die nachfolgenden kristallinen Produkte dient. Der genaue Reaktionsablauf, der zur Bildung von amorphem Calciumcarbonat (ACC) führt, ist nicht bekannt. Ziel dieser Arbeit war die Entwicklung einer Fällungstechnik, die die Beobachtung der Bildungskinetik von ACC durch Lichtstreuung ermöglicht. In Fällungsexperimenten wird gezeigt, dass die Fällung unter nicht-turbulenten Bedingungen zur Bildung von amorphem Calciumcarbonat führt. Hinsichtlich der Basen- und Alkylcarbonatmenge, die äquivalent oder im Überschuss zur Calciumionenkonzentration eingesetzt wird, entstehen zwei verschiedene Fällungsprodukte. In Bezug auf ihre chemische Zusammensetzung, thermische und mechanische Eigenschaften werden diese charakterisiert. In beiden Fällen wird ein amorphes CaCO3 mit einem Wassergehalt von 0,5 mol/L pro Mol CaCO3 erhalten. Die in situ Generierung von Carbonat führt zur Bildung von sphärischem amorphem Calciumcarbonat, das eine gewisse Tendenz zur Koazervation zeigt. Die bei gleichem Reaktionsumsatz beobachtete Temperaturabhängigkeit des Partikelradius konnten wir unter Annahme einer Mischungslücke mit unterer kritischer Mischungstemperatur interpretieren. Für die Bildung von amorphem Calciumcarbonat schlagen wir daher einen Mechanismus via binodaler flüssig-flüssig Entmischung vor. Nach einer kurzen Keimbildungsperiode können flüssige Tröpfchen aus wasserhaltigem CaCO3 wachsen und dann infolge von stetigem Wasserverlust glasartig erstarren und so amorphes Calciumcarbonat bilden. Bekräftigt wird dieses Modell durch die Wachstumskinetik, die mittels Lichtstreuung und SAXS verfolgt worden ist. In den Fällungsversuchen sind je nach Reaktionsbedingungen, zwei verschiedene Zeitgesetze des Teilchenwachstums erkennbar: Bei schneller Freisetzung von Carbonat liegt ein parabolischer Verlauf des Radienwachstums vor; hingegen führt eine langsame Freisetzung von Carbonat zu einem linearen Wachstum der Radien. Diese Abhängigkeiten lassen sich im Rahmen der bekannten Kinetik einer flüssig-flüssig Entmischung deuten. Ferner wird der Einfluss von doppelthydrophilen Blockcopolymeren (PEO-PMAA) auf die Teilchengröße und die Kinetik der Bildung von amorphem Calciumcarbonat untersucht. Zum Einsatz kommen zwei verschiedene Blockcopolymere, die sich in der Länge des PEO-Blocks unterscheiden. Im Fällungsexperiment führt das in sehr kleinen Konzentrationen vorliegende Blockcopolymere zur Stabilisierung von kleineren Partikeln. Das Blockcopolymer mit der längeren PEO-Einheit weist eine größere Effizienz auf. Die Ergebnisse lassen sich durch Annahme von Adsorption des Polymers an der Oberfläche interpretieren. Der Einfluss der doppelthydrophilen Blockcopolymere auf die Bildung von ACC deutet darauf, dass amorphes Calciumcarbonat eine komplexere Rolle als lediglich die eines Calciumcarbonatspeichers für das spätere Wachstum kristalliner Produkte einnimmt. Für die Wirkung von Polymerzusätzen muss somit nicht nur die Wechselwirkung mit den gegen Ende gebildeten Kristalle betrachtet werden, sondern auch der Einfluss, den das Polymer auf die Bildung des amorphen Calciumcarbonats hat. Die hier neu entwickelte Methode bietet die Möglichkeit, auch für komplexere Polymere, wie z.B. extrahierte Proteine, den Einfluss auf die Bildung der amorphen Vorstufe zu untersuchen.

Assessment of occupational exposures to organic chemicals in a plastics manufacturing facility

The objective of this dissertation was to design and implement strategies for assessment of exposures to organic chemicals used in the production of a styrene-butadiene polymer at the Texas Plastics Company (TPC). Linear statistical retrospective exposure models, univariate and multivariate, were developed based on the validation of historical industrial hygiene monitoring data collected by industrial hygienists at TPC, and additional current industrial hygiene monitoring data collected for the purposes of this study. The current monitoring data served several purposes. First, it provided information on current exposure data, in the form of unbiased estimates of mean exposure to organic chemicals for each job title included. Second, it provided information on homogeneity of exposure within each job title, through the use of a carefully designed sampling scheme which addressed variability of exposure both between and within job titles. Third, it permitted the investigation of how well current exposure data can serve as an evaluation tool for retrospective exposure estimation. Finally, this dissertation investigated the simultaneous evaluation of exposure to several chemicals, as well as the use of values below detection limits in a multivariate linear statistical model of exposures. ^

Estudo da redução de arrasto induzido por polímeros em escoamentos internos turbulentos em dutos

The flows turbulent and laminar are present in various applications of engineering and one of the villain of energy loss big is the surface friction. Currently, there are several research aimed for the study of reducing drag (DR) with the objective of developing effective methods to reduce the friction. Regardless of numerous research carried out until today, the phenomenon DR still remains in study not it is fully understood. This paper studied the drag reduction by polymer induction in turbulent internal flows in ducts. We constructed a testing bench to perform the analysis of drag reduction, the bench has basically two manometers with a 8.5 psi full scale, a peripheral pump 0.5 HP, an acrylic tank, valves and tubes pvc and is situated in the Laboratory Fluid Mechanics UFRN. Were used as polymer additives to polyethylene glycol 4000, the Polyox WSR N60K, Polyox WSR 301 and Polyox WSR 205. The rationale for the choice of these polymers is their wide application in situations requiring greater energy efficiency, such as the addition reducing polymers for the jet used by the fire department to achieve greater distances. The induced drag reduction polymers is investigated from the turbulent flow analysis, with Reynolds number in a range between 2×104

Estudo da redução de arrasto induzido por polímeros em escoamentos internos turbulentos em dutos

The flows turbulent and laminar are present in various applications of engineering and one of the villain of energy loss big is the surface friction. Currently, there are several research aimed for the study of reducing drag (DR) with the objective of developing effective methods to reduce the friction. Regardless of numerous research carried out until today, the phenomenon DR still remains in study not it is fully understood. This paper studied the drag reduction by polymer induction in turbulent internal flows in ducts. We constructed a testing bench to perform the analysis of drag reduction, the bench has basically two manometers with a 8.5 psi full scale, a peripheral pump 0.5 HP, an acrylic tank, valves and tubes pvc and is situated in the Laboratory Fluid Mechanics UFRN. Were used as polymer additives to polyethylene glycol 4000, the Polyox WSR N60K, Polyox WSR 301 and Polyox WSR 205. The rationale for the choice of these polymers is their wide application in situations requiring greater energy efficiency, such as the addition reducing polymers for the jet used by the fire department to achieve greater distances. The induced drag reduction polymers is investigated from the turbulent flow analysis, with Reynolds number in a range between 2×104

Nanomorphology influence on the light conversion mechanisms in highly efficient diketopyrrolopyrrole based organic solar cells

In this work, diketopyrrolopyrrole-based polymer bulk heterojunction solar cells with inverted and regular architecture have been investigated. The influence of the polymer:fullerene ratio on the photoactive film nanomorphology has been studied in detail. Transmission Electron Microscopy and Atomic Force Microscopy reveal that the resulting film morphology strongly depends on the fullerene ratio. This fact determines the photocurrent generation and governs the transport of free charge carriers. Slight variations on the PCBM ratio respect to the polymer show great differences on the electrical behavior of the solar cell. Once the polymer:fullerene ratio is accurately adjusted, power conversion efficiencies of 4.7% and 4.9% are obtained for inverted and regular architectures respectively. Furthermore, by correlating the optical and morphological characterization of the polymer:fullerene films and the electrical behavior of solar cells, an ad hoc interpretation is proposed to explain the photovoltaic performance as a function of this polymer:blend composition.

Statistical properties of turbulence: An overview

We present an introductory overview of several challenging problems in the statistical characterization of turbulence. We provide examples from fluid turbulence in three and two dimensions, from the turbulent advection of passive scalars, turbulence in the one-dimensional Burgers equation, and fluid turbulence in the presence of polymer additives.

Synthesis and characterization of white-light-emitting polyfluorenes containing orange phosphorescent moieties in the side chain

Two orange phosphorescent iridium complex monomers, 9-hexyl-9-(iridium (III)bis(2-(4'-fluorophenyl)-4-phenylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-PIr) and 9-hexyl-9-(iridium(III)bis(2-(4'-fluorophenyl)-4-methylquinoline-N, C-2')(tetradecanedionate-11,13))-2,7-dibromofluorene (Br-MIr), were successfully synthesized. The Suzuki polycondensation of 2,7-bis(trimethylene boronate)-9,9-dioctylfluorene with 2,7-dibromo-9,9-dioetylfluorene and Br-Plr or Br-MIr afforded two series of copolymers, PIrPFs and MIrPFs, in good yields, in which the concentrations of the phosphorescent moieties were kept small (0.5-3 mol % feed ratio) to realize incomplete energy transfer. The photoluminescence (PL) of the copolymers showed blue- and orange-emission peaks. A white-light-emitting diode with a configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)/PIr05PF (0.5 mol % feed ratio of Br-PIr)/Ca/Al exhibited a luminous efficiency of 4.49 cd/A and a power efficiency of 2.35 lm/W at 6.0 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.46, 0.33). The CIE coordinates were improved to (0.34, 0.33) when copolymer MIr10PF (1.0 mol % feed ratio of Br-MIr) was employed as the white-emissive layer. The strong orange emission in the electroluminescence spectra in comparison with PL for these kinds of polymers was attributed to the additional contribution of charge trapping in the phosphorescent dopants.

White electroluminescence from a poly(N-vinylcarbazole) layer doped with CdSe/CdS core-shell quantum dots

Hybrid organic/inorganic white light-emitting diodes (LEDs) were fabricated of semiconductor polymer poly(N-vinylcarbazole) (PVK) doped with CdSe/CdS core-shell semiconductor quantum dots (QDs). The device, with a structure of indium-tin-oxide (ITO)vertical bar 3,4-polyethylene-dioxythiophene- polystyrene sulfonate (PEDOT:PSS)vertical bar PVK:CdSe/CdS vertical bar Al, emitted a pure white light spanning the whole visible region from 400 to 800 nm. The Commission Internationale del'Eclairage coordinates (CIE) remained at x = 0.33, y = 0.34 at wide applied voltages. The maximum brightness and electroluminescence (EL) efficiency reached 180 cd m(-2) at 19 V and 0.21 cd A(-1) at current density of 2 mA cm(-2), respectively. The realization of the pure white light emission is attributed to the incomplete energy and charge transfer from PVK to CdSe/CdS core-shell QDs.

Effect of cavitations on brittle-ductile transition of particle toughened thermoplastics

In this study, we established a correlation between cavitations volume and the brittle-ductile transition (BDT) for particle toughened thermoplastics. The brittle-ductile transition temperature (T-BD) was calculated as a function of T* and interparticle distance (ED), respectively, where T* was a parameter related to the volume of cavitations. The results showed that the smaller the cavitations volume, the higher the brittle-ductile transition temperature. The calculations correlated well with the experimental data. With respect to rubber particle, the rigid particle was too hard to be voided during deformation, thereby the TED of the blend was much higher than that of rubber particle toughened thermoplastic. This was a main reason that rubber particle could toughen thermoplastics effectively, whereas rigid particle could not.

Brittle-tough transition in PP/EPDM blends: effects of interparticle distance and tensile deformation speed

The toughness of polypropylene (PP)/ethylene-propylene-diene monomer rubber (EPDM) blends containing various EPDM contents as a function of the tensile speed was studied. The toughness of the blends was determined from the tensile fracture energy of the side-edge notched samples. A sharp brittle-tough transition was observed in the fracture energy versus interparticle distance (ID) curves when the crosshead speed < 102.4 mm/min. It was observed that the brittle-ductile transition of PP/EPDM blend occurred either by reducing ID or by decreasing the tensile speed. The correlation between the critical interparticle distance and tensile deformation rate was compared with that between the critical interparticle distance and temperature for PP/EPDM blends. (C) 2000 Elsevier Science Ltd. All rights reserved.

Optimization of the processing of HNBR/organoclay nanocomposite

In the current investigation, rubber/clay nanocomposites were prepared by two different methods using hydrogenated nitrile butadiene rubber (HNBR) and the organoclay namely Cloisite 15A (C15A). A new novel approach involving swelling of C15A by ulltrasonication in HNBR solution has been carried out for improving the exfoliation and compatibilization of organoclays with HNBR matrix. With the addition of 5phr of clay, the elongation at break and tear strength improved by 16% and 24% respectively. The effect of coupling agents namely amino functional silane and tetrasulfido silane on the nanocomposites have been investigated. The elongation at break and tear strength improved by 46% and 77% respectively with the use of silanes. The improvement in the mechanical properties attributes to improved interaction between the organoclays and HNBR matrix. This interaction has been studied by X-ray diffraction and transmission electron microscope. Pre-dispersion technique clearly suggests very good improvement in the dispersion and properties due to better filler-rubber compatibility. © 2010 American Institute of Physics.

Hard coatings on elastomers for reduced permeability and increased wear resistance

In this study, three different elastomers, namely hydrogenated nitrile butadiene rubber, fluoroelastomer and silicone, have been subjected to two different hard metallised coatings by ion implantation process. The three different elastomers are commonly used in various seal applications, where reduced wear and gas permeability are essential in maintaining seal performance and functionality. Samples of these rubbers have been coated with chromium coating in one set of tests. In the second set of tests, samples of elastomers have been coated with tungsten carbide coating being deposited on all the three different elastomers. Wear, gas permeability and mechanical behaviour of the coated samples were compared with each other and with the control uncoated elastomers. All the coated samples showed good reduction in gas permeability. With the use of metallised coatings, there has been improved resistance to wear in all the coated samples. Adhesion strength and effect of coating on the elastomer have been investigated by mechanical testing. Mechanical tests revealed good adhesion of metal coatings on all the rubber samples, and there was no detrimental effect on the mechanical properties after coating. © 2012 Institute of Materials, Minerals and Mining.

Low Temperature Curing of NBR for Property Improvement

Zinc salts of ethyl, isopropyl, and butyl xanthates are prepared in the laboratory, and the effect of these xanthates with zinc diethyl dithiocarbamate (ZDC) on the vulcanization of HAF-filled nitrile butadiene rubber (NBR) compounds has been studied at different temperatures. The cure times of these compounds have been compared with that of NBR compounds containing TMTD/MBTS. The rubber compounds with the three xanthate accelerators and ZDC are cured at various temperatures from 60 to 150°C. The sheets are molded and properties such as tensile strength, tear strength, cross-link density, elongation at break, compression set, abrasion resistance, flex resistance, etc. have been evaluated. The properties show that zinc salt of the xanthate/ZDC accelerator system has a positive synergistic effect on the cure rate and mechanical properties of NBR compounds.

Polymeric complexesSynthesis, Characterization and Analytical Applications

As the application of polymeric complexes is enormous, there exists a continuing interest in the synthesis and characterization of these complexes. The synthetic and characterization parts are very important in an academic point of view. Further in an application point of view also polymeric ligands/complexes are gaining attention.The thesis is divided in to six chapters, in which the first chapter gives an introduction along with a brief review on polymeric ligands/ complexes. The second chapter explains the different procedure adopted for the whole work along with the details of the reagents/ instruments used. The third chapter gives a report of the detailed study regarding the synthesis and characterization of eighteen complexes. While the fourth chapter is a report of the ion removal studies using three polymeric ligands, the fifth chapter explains the development of a polymeric complex as ion selective electrode material for the fabrication of a CC ion selective electrode. The sixth chapter presents the summary and tables, figures and references are given separately at the end.

Efeito da adição dos azocorantes DR73 e DB79 nas propriedades do poli(metacrilato de metila)

Currently new polymeric materials have been developed to replace other of traditionally materials classes. The use of dyes allows to expand and to diversify the applications in the polymeric materials development. In this work the behavior and ability of azo dyes Disperse Blue 79 (DB79) and Disperse Red 73 (DR73) on poly(methyl methacrylate) (PMMA) were studied. Two types of mixtures were used in the production of masterbatches: 1) rheometer 2) solution. Processing by extrusion-blow molding of PMMA was carried out in order to evaluate the applications of polymeric films. Thermal analysis were performed by thermogravimetry to evaluate polymer and azo dyes thermal stability. Colorimetric analysis were obtained through monitoring the spectral variations associated with sys/trans/anti azo dyes isomerization process Colorimetric data were treated and evaluated in accordance to the color system RGB and CIEL*ab, by monitoring the color change as function of time. Mechanical properties, characterized by tensile tests, were evaluated and correlated with the presence and content of azo dyes in the samples. Analyses by scanning electronic microscopy (SEM) were performed on the surfaces of samples to check the azo dye dispersion after the mixing process. It was concluded that the production of PMMA/azo dyes is possible and feasible, and the mixtures produced had synergy of properties for use in various applications