Clay-containing block copolymer nanocomposites with aligned morphology prepared by extrusion

Clay-containing nanocomposites of polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (SEBS) copolymers having cylindrical domains were obtained by melt extrusion using a tape die. One type of sample (SEBS-MA) had maleic anhydride attached to the middle block. Two types of organoclays were added, namely Cloisite 20A and Cloisite 30B. Small angle X-ray scattering and transmission electron microscopy (TEM) analyses showed that the addition of 20A clay to SEBS and SEBS-MA resulted in nanocomposites with intercalated and partially exfoliated structures, respectively. The addition of 30B clay to SEBS and SEBS-MA promoted the formation of composites containing relatively large micron-sized and partially exfoliated clay particles, respectively. Our TEM analysis revealed that clay particles embedded in SEBS are preferably in contact with the polystyrene cylindrical domains, while in SEBS-MA they are in contact with the maleated matrix. The extrusion processing promoted alignment of the axes of the polystyrene cylinders along the extrusion direction in all samples, and the basal planes of the clay particles were mostly parallel to the main external surfaces of the extruded tapes. © 2013 Society of Chemical Industry.

Morphology of accessory genital glands of spotted paca(Agouti paca Linnaeus, 1766)

The spotted paca is the second largest rodent in Brazil, where it is of great economic interestin impoverished regions in view of its prominence as a low-cost source of protein. Littleis known about the morphology of the accessory genital glands of this species. Thus, westudied the position and morphology of the genitals in ten adult male spotted pacas. Theanimals were divided into two groups, five animals were used for fixing of samples in 10%aqueous formaldehyde for macroscopic studies and the other five animals were designatedfor microscopic analysis. These were arranged in pairs and had the vesicular, prostate,coagulating and bulbourethral glands identified, being structured as mucous glands, whichlead into the pelvic urethra. It was concluded that the accessory genital glands found in thepaca are the same as those found in most rodents, showing similar histological aspects

Effects of trophic levels (chlorophyll and phosphorous content) in three different water bodies (urban lake, reservoir and aquaculture facility) on gill morphology of Nile tilapia (Oreochromis niloticus)

Histological and ultrastructural analyses of gills were observed in Nile tilapia collected from three different waterbodies in southeast Brazil: an urban lake in a park in the city of São Paulo, a reservoir in a rural city, and a commercial aquaculture facility. These aterbodies were analyzed and classified as hypereutrophic, eutrophic, and supereutrophic, respectively, with 310.00, 94.00, 28.00 of phosphate (PO2_ 4 lg L _1) and 65.49, 24.95, 12.83 of chlorophyll (lg L _1). A significant difference in the histological alterations index (HAI) was observed only in fish from the urban lake, with the presence of cell hypertrophy, hyperplasia, aneurism, and other alterations. When compared to the other groups, a large quantity of rodlet cells was also observed in the urban group. These results demonstrate the correlation of eutrophic states of water with gill morphology. Also discussed is the premise that large amounts of organic material dissolved in water can alter the morphology of the fish gills

The evolutionary implications of hemipenial morphology of rattlesnake Crotalus durissus terrificus (Laurent, 1768) (Serpentes: Viperidae: Crotalinae)

Most amniotes vertebrates have an intromittent organ to deliver semen. The reptile Sphenodon and most birds lost the ancestral penis and developed a cloaca-cloaca mating. Known as hemipenises, the copulatory organ of Squamata shows unique features between the amniotes intromittent organ. They are the only paired intromittent organs across amniotes and are fully inverted and encapsulated in the tail when not in use. The histology and ultrastructure of the hemipenes of Crotalus durissus rattlesnake is described as the evolutionary implications of the main features discussed. The organization of hemipenis of Crotalus durissus terrificus in two concentric corpora cavernosa is similar to other Squamata but differ markedly from the organization of the penis found in crocodilians, testudinata, birds and mammals. Based on the available data, the penis of the ancestral amniotes was made of connective tissue and the incorporation of smooth muscle in the framework of the sinusoids occurred independently in mammals and Crotalus durissus. The propulsor action of the muscle retractor penis basalis was confirmed and therefore the named should be changed to musculus hemipenis propulsor.The retractor penis magnus found in Squamata has no homology to the retractor penis of mammals, although both are responsible for the retraction of the copulatory organ

Active tectonics in the NW-German Basin: Evidence from correlations between the modern landscape and deep geological structures (Lower Saxony, river Hunte)

KurzfassungIm Einzugsgebiet der Hunte (NW-Deutsches Becken, Niedersachsen) wurde untersucht, ob die Landschaftsgenese durch tektonische Bewegungen der Oberkruste beeinflußt ist. Krustenbewegungen führten im Bereich einer Hauptschollengrenze zu einer Hebung der weichselzeitlichen Niederterrasse (durchschnittliche Hebungssrate von ~0,5 mm/a über die letzten 12000 Jahre). Tektonischer Einfluß auf die heutige Landoberfläche ist über einem permischen Salzkissen zu verzeichnen, wo sich das Gefälle der holozänen Aue umkehrt. Krustenbewegungen haben mit großer Wahrscheinlichkeit Vorzugsrichtungen verursacht, die an der Tertiärbasis und in der heutigen Landschaft nachweisbar sind (0-5° und 90-95°). Das Abfließen der Hunte nach Norden scheint durch eine aktive, nordwärts gerichtete Kippung des NW-Deutschen Beckens verursacht zu sein. Hohe lineare Korrelationskoeffizienten zwischen Tiefenlage der Tertiärbasis und Höhenlage der heutigen Landoberfläche weisen auf eine aktive Kippung des Beckens hin. Beckensubsidenz hat möglicherweise die Akkumulation der weichselzeitlichen Niederterrasse gesteuert, da eine Übereinstimmung zwischen rezenter Beckensubsidenz und durchschnittlicher Sedimentationsrate des Niederterrassenkörpers besteht. Untersuchungen an einer geschlossenen Hohlform deuten auf eine aktive Sackungsstruktur hin, da sich Anomalien des geologischen Untergrundes mit der topographischen Lage der Struktur decken.

Dietary strategies to minimize the detrimental impact of weaning on gut morphology, physiology and microbiota of piglets

Weaning is a crucial period in the management of piglets. In modern piggeries economic interest make weaning age decrease more and more and the detrimental consequences of weaning have as much importance as earlier the weaning occurs. The risk of development of post-weaning diarrhea (PWD) in piglets is high and PWD is the cause of serious economic losses in pig herds. In the past the supplementation of the feed given after weaning with growth promoters antibiotics, in order to keep PWD under control, used to be a common practice, but their usage has been banned in EU since 2006. This measure led to the investigation of alternative suitable feed supplements that would be reasonably efficient in protecting and sustaining animal health and performance. Aim of this thesis was to evaluate the effect of some different alternatives to growth-promoters antibiotics on weaning piglets and to assess if some of them could be considered as valuables options to replace auxinic in animal feeding. The study is composed by four experimental trials. The first one aims to identify mechanisms involved in the auxinic effects of antibiotics in the diets; the following three evaluate the addition butyric acid, tryptophan, and nitrate as alternative to in-feed antimicrobials. Although some results are controversial, it appears from the data presented that the alternatives to in-feed antibiotics considered may exert positive effects on some zootechnical and health parameters on piglet in the post-weaning period. Anyway, the mechanism of action and the interaction with microbiota of such additives should be investigated inside out because many effects remains poorly understood.

The physical city and the urban structure: detecting amenity zones and applying urban morphology to New York

The city is a collection of built structures and infrastructure embedded in socio-cultural processes: any investigation into a city’s transformations involves considerations on the degree to which its composite elements respond to socio-economical changes. The main purpose of this research is to investigate how transformations in the functional requirements of New York’s society have spurred, since the 1970s, changes in both the city’s urban structure and physical form. The present work examines the rise of Amenity Zones in New York, and investigates the transformations that have occurred in New York’s built environment since the 1970s. By applying qualitative measures and analyzing the relationship between urban amenities and the creative class, the present work has investigated changes in the urban structure and detected a hierarchical series of amenity zones classes, namely, Super Amenity Zones (SAZs), Nodal Amenity Zones (NAZs) and Peripheral Amenity Zones (PAZs). This series allows for a more comprehensive reading of the urban structure in a complex city like New York, bringing advancements to the amenity zone’s methodology. In order to examine the manner in which the other component of the city, the physical form, has changed or adapted to the new socio-economic condition, the present research has applied Conzenian analysis to a select study area, Atlantic Avenue. The results of this analysis reveal that, contrary to the urban structure, which changes rapidly, the physical form of New York is hard to modify completely, due to the resilience of the town plan and its elements, and to preservation laws; the city rather adapts to socio-economical changes through process of adaptive reuses or conversion. Concluding, this research has examined the dialectic between the ever-changing needs of society and the complexity of the built environment and urban structure, showing the different degrees to which the urban landscape modifies, reacts and sometimes adapts to the population’s functional requirements.

The influence of film morphology on solution processed organic field-effect transistors

Organic field-effect transistors (OFETs) are becoming interesting owing to their prospective application as cheap, bendable and light weight electronic devices rnlike flexible displays. However, the bottleneck of OFETs is their typically low charge carrier mobilities. An effective and crucial route towards circumventing thisrnhurdle is the control of organic semiconductor thin film morphology which critically determine charge carrier transport. In this work, the influence of film morphologyrnis highlighted together with its impact on OFET transistor performance.

Morphology and charge transport in conjugated polymers

To assist rational compound design of organic semiconductors, two problems need to be addressed. First, the material morphology has to be known at an atomistic level. Second, with the morphology at hand, an appropriate charge transport model needs to be developed in order to link charge carrier mobility to structure.rnrnThe former can be addressed by generating atomistic morphologies using molecular dynamics simulations. However, the accessible range of time- and length-scales is limited. To overcome these limitations, systematic coarse-graining methods can be used. In the first part of the thesis, the Versatile Object-oriented Toolkit for Coarse-graining Applications is introduced, which provides a platform for the implementation of coarse-graining methods. Tools to perform Boltzmann inversion, iterative Boltzmann inversion, inverse Monte Carlo, and force-matching are available and have been tested on a set of model systems (water, methanol, propane and a single hexane chain). Advantages and problems of each specific method are discussed.rnrnIn partially disordered systems, the second issue is closely connected to constructing appropriate diabatic states between which charge transfer occurs. In the second part of the thesis, the description initially used for small conjugated molecules is extended to conjugated polymers. Here, charge transport is modeled by introducing conjugated segments on which charge carriers are localized. Inter-chain transport is then treated within a high temperature non-adiabatic Marcus theory while an adiabatic rate expression is used for intra-chain transport. The charge dynamics is simulated using the kinetic Monte Carlo method.rnrnThe entire framework is finally employed to establish a relation between the morphology and the charge mobility of the neutral and doped states of polypyrrole, a conjugated polymer. It is shown that for short oligomers, charge carrier mobility is insensitive to the orientational molecular ordering and is determined by the threshold transfer integral which connects percolating clusters of molecules that form interconnected networks. The value of this transfer integral can be related to the radial distribution function. Hence, charge mobility is mainly determined by the local molecular packing and is independent of the global morphology, at least in such a non-crystalline state of a polymer.

Hyperbranched polyether polyols as building blocks for complex macromolecular architectures

The present thesis deals with the development of new branched polymer architectures containing hyperbranched polyglycerol. Materials investigated include hyperbranched oligomers, hyperbranched polyglycerols containing functional initiator-cores at the focal point, well-defined linear-hyperbranched block copolymers and also negatively charged hyperbranched polyelectrolytes.rnHyperbranched oligoglycerols (DPn = 7 and 14) have been synthesized for the first time. The materials show narrow polydispersity (Mw/Mn ca. 1.45) and a very low content in cyclic homopolymers. 13C NMR evidences the dendritic structure of the oligomers and the DB could be calculated (44% and 52%). These new oligoglycerols were compared with the industrial products obtained by polycondensation which exhibit narrow polydispersity (Mw/Mn<1.3) butrnmultimodal distribution in SEC. Detailed 13C NMR and Maldi-ToF studies reveal the presence of branched units and cyclic compounds. In comparison, the hyperbranched oligoglycerols comprise a very low proportion of cyclic homopolymer which render them very interesting materials for biomedical applications for example.rnThe site isolation of the core moiety in dendritic structure offers intriguing potential with respect to peculiar electro-optical properties. Various initiator-cores (n-alkyl amines, UVabsorbing amines and benzophenone) for the ROMBP of glycidol have been tested. The bisglycidolized amine initiator-cores show the best control over the molecular weight and the molecular weight distribution. The photochemical analyses of the naphthalene containingrnhyperbranched polyglycerols show a slight red shift, a pronounced hypochromic effect (decrease of the intensity of the band) compared with the parent model compound and the formation of a relative compact structure. The benzophenone containing polymers adopt an open structure in polar solvents. The fluorescence measurements show a clear “dendritic effect” on the fluorescence intensities and the quantum yield of the encapsulated benzophenone.rnA convenient 3-step strategy has been developed for the preparation of well-defined amphiphilic, linear-hyperbranched block copolymers via hypergrafting. The procedure represents a combination of carbanionic polymerization with the alkoxide-based, controlled ring-opening multibranching polymerization of glycidol. Materials consisting of a polystyrene linear block and a hyperbranched polyglycerol block exhibit narrow polydispersity (1.01-1.02rnfor 5.4% to 27% wt. PG and 1.74 for 52% wt. PG) with a high grafting efficiency. The strategy was also extended to materials with a linear polyisoprene block.rnDetailed investigations of the solution properties of the block copolymers with linear polystyrene blocks show that block copolymer micelles are stabilized by the highly branched block. The morphology of the aggregates is depending on the solvent: in chloroform monodisperse spherical shape aggregates and in toluene ellipsoidal aggregates are formed. On graphite these aggregates show interesting features, giving promising potential applications with respect to the presence of a very dense, functional and stable hyperbranched block.rnThe bulk morphology of the linear-hyperbranched block copolymers has been investigated. The materials with a linear polyisoprene block only behave like complex liquids due to the low Tg and the disordered nature of both components. For the materials with polystyrene, only the sample with 27% wt. hyperbranched polyglycerol forms some domains showing lamellae.rnThe preparation of hyperbranched polyelectrolytes was achieved by post-modification of the hydroxyl groups via Michael addition of acrylonitrile, followed by hydrolysis. In aqueous solution materials form large aggregates with size depending on the pH value. After deposition on mica the structures observed by AFM show the coexistence of aggregates andrnunimers. For the low molecular weight sample (PG 520 g·mol-1) extended and highly ordered terrace structures were observed. Materials were also successfully employed for the fabrication of composite organic-inorganic multilayer thin films, using electrostatic layer-bylayer self-assembly coupled with chemical vapor deposition.

Morphology of leds by atomic force microscopy

The concern of this work is to present the characterization of blue emitting GaN-based LED structures by means of Atomic Force Microscopy. Here we show a comparison among the samples with different dislocation densities, in order to understand how the dislocations can affect the surface morphology. First of all we have described the current state of art of the LEDs in the present market. Thereafterwards we have mentioned in detail about the growth technique of LED structures and the methodology of the characterization employed in our thesis. Finally, we have presented the details of the results obtained on our samples studied, followed by discussions and conclusions. L'obiettivo di questa tesi é quello di presentare la caratterizzazione mediante Microscopia a Forza Atomica di strutture di LED a emissione di luce blu a base di nitruro di gallio (GaN). Viene presentato un confronto tra campioni con differente densità di dislocazioni, allo scopo di comprendere in che modo la presenza di dislocazioni influisce sulla morfologia della superficie. Innanzitutto, viene descritto il presente stato dell'arte dei LED. Successivamente, sono forniti i dettagli riguardanti la tecnica di crescita delle strutture dei LED e il metodo di caratterizzazione adottato. Infine, vengono mostrati e discussi i risultati ottenuti dallo studio dei campioni, seguiti dalle conclusioni.

Morphology control in metallocene-catalyzed polyolefin synthesis

The main aim of the work presented in this dissertation was the morphology control in metallocene-catalyzed polyolefin synthesis. This was studied by selective immobilization techniques on a variety of supports such as porous polyurethane particles (Chapter 3), electrospun fibers (Chapter 4 and 5), inorganic-organic hybrid core-shell particles (Chapter 6) and hollow silica particles (Chapter 7). Another aspect of this dissertation was modulating a catalytic activity by controlling a size of boron-based cocatalysts (Chapter 8).

Crystallization and morphology of the PLLA phase within random poly (L-lactide-ran-ɛ-caprolactone)

This work has mainly focused on the poly (L-lactide) (PLLA) which is a material for multiple applications with performances comparable to those of petrochemical polymers (PP, PS, PET, etc. ...), readily recyclable and also compostable. However, PLLA has certain shortcomings that limit its applications. It is a brittle, hard polymer with a very low elongation at break, hydrophobic, exhibits low crystallization kinetics and takes a long time to degrade. The properties of PLLA may be modified by copolymerization (random, block, and graft) of L-lactide monomers with other co-monomers. In this thesis it has been studied the crystallization and morphology of random copolymers poly (L-lactide-ran-ε-caprolactone) with different compositions of the two monomers since the physical, mechanical, optical and chemical properties of a material depend on this behavior. Thermal analyses were performed by differential scanning calorimetry (DSC) and thermogravimetry (TGA) to observe behaviors due to the different compositions of the copolymers. The crystallization kinetics and morphology of poly (L-lactide-ran-ε-caprolactone) was investigated by polarized light optical microscopy (PLOM) and differential scanning calorimetry (DSC). Their thermal behavior was observed with crystallization from melt. It was observed that with increasing amounts of PCL in the copolymer, there is a decrease of the thermal degradation. Studies on the crystallization kinetics have shown that small quantities of PCL in the copolymer increase the overall crystallization kinetics and the crystal growth rate which decreases with higher quantities of PCL.

Unraveling efficiency-limiting processes in organic solar cells by ultrafast spectroscopy - impact of chemical structure and morphology on photophysics and efficiency

Diese Arbeit widmet sich der Untersuchung der photophysikalischen Prozesse, die in Mischungen von Elektronendonoren mit Elektronenakzeptoren zur Anwendung in organischen Solarzellen auftreten. Als Elektronendonoren werden das Copolymer PBDTTT-C, das aus Benzodithiophen- und Thienothiophene-Einheiten besteht, und das kleine Molekül p-DTS(FBTTh2)2, welches Silizium-überbrücktes Dithiophen, sowie fluoriertes Benzothiadiazol und Dithiophen beinhaltet, verwendet. Als Elektronenakzeptor finden ein planares 3,4:9,10-Perylentetracarbonsäurediimid-(PDI)-Derivat und verschiedene Fullerenderivate Anwendung. PDI-Derivate gelten als vielversprechende Alternativen zu Fullerenen aufgrund der durch chemische Synthese abstimmbaren strukturellen, optischen und elektronischen Eigenschaften. Das gewichtigste Argument für PDI-Derivate ist deren Absorption im sichtbaren Bereich des Sonnenspektrums was den Photostrom verbessern kann. Fulleren-basierte Mischungen übertreffen jedoch für gewöhnlich die Effizienz von Donor-PDI-Mischungen.rnUm den Nachteil der PDI-basierten Mischungen im Vergleich zu den entsprechenden Fulleren-basierten Mischungen zu identifizieren, werden die verschiedenen Donor-Akzeptor-Kombinationen auf ihre optischen, elektronischen und strukturellen Eigenschaften untersucht. Zeitaufgelöste Spektroskopie, vor allem transiente Absorptionsspektroskopie (TA), wird zur Analyse der Ladungsgeneration angewendet und der Vergleich der Donor-PDI Mischfilme mit den Donor-Fulleren Mischfilmen zeigt, dass die Bildung von Ladungstransferzuständen einen der Hauptverlustkanäle darstellt.rnWeiterhin werden Mischungen aus PBDTTT-C und [6,6]-Phenyl-C61-buttersäuremethylesther (PC61BM) mittels TA-Spektroskopie auf einer Zeitskala von ps bis µs untersucht und es kann gezeigt werden, dass der Triplettzustand des Polymers über die nicht-geminale Rekombination freier Ladungen auf einer sub-ns Zeitskala bevölkert wird. Hochentwickelte Methoden zur Datenanalyse, wie multivariate curve resolution (MCR), werden angewendet um überlagernde Datensignale zu trennen. Zusätzlich kann die Regeneration von Ladungsträgern durch Triplett-Triplett-Annihilation auf einer ns-µs Zeitskala gezeigt werden. Darüber hinaus wird der Einfluss des Lösungsmitteladditivs 1,8-Diiodooctan (DIO) auf die Leistungsfähigkeit von p-DTS(FBTTh2)2:PDI Solarzellen untersucht. Die Erkenntnisse von morphologischen und photophysikalischen Experimenten werden kombiniert, um die strukturellen Eigenschaften und die Photophysik mit den relevanten Kenngrößen des Bauteils in Verbindung zu setzen. Zeitaufgelöste Photolumineszenzmessungen (time-resolved photoluminescence, TRPL) zeigen, dass der Einsatz von DIO zu einer geringeren Reduzierung der Photolumineszenz führt, was auf eine größere Phasentrennung zurückgeführt werden kann. Außerdem kann mittels TA Spektroskopie gezeigt werden, dass die Verwendung von DIO zu einer verbesserten Kristallinität der aktiven Schicht führt und die Generation freier Ladungen fördert. Zur genauen Analyse des Signalzerfalls wird ein Modell angewendet, das den gleichzeitigen Zerfall gebundener CT-Zustände und freier Ladungen berücksichtigt und optimierte Donor-Akzeptor-Mischungen zeigen einen größeren Anteil an nicht-geminaler Rekombination freier Ladungsträger.rnIn einer weiteren Fallstudie wird der Einfluss des Fullerenderivats, namentlich IC60BA und PC71BM, auf die Leistungsfähigkeit und Photophysik der Solarzellen untersucht. Eine Kombination aus einer Untersuchung der Struktur des Dünnfilms sowie zeitaufgelöster Spektroskopie ergibt, dass Mischungen, die ICBA als Elektronenakzeptor verwenden, eine schlechtere Trennung von Ladungstransferzuständen zeigen und unter einer stärkeren geminalen Rekombination im Vergleich zu PCBM-basierten Mischungen leiden. Dies kann auf die kleinere Triebkraft zur Ladungstrennung sowie auf die höhere Unordnung der ICBA-basierten Mischungen, die die Ladungstrennung hemmen, zurückgeführt werden. Außerdem wird der Einfluss reiner Fullerendomänen auf die Funktionsfähigkeit organischer Solarzellen, die aus Mischungen des Thienothienophen-basierenden Polymers pBTTT-C14 und PC61BM bestehen, untersucht. Aus diesem Grund wird die Photophysik von Filmen mit einem Donor-Akzeptor-Mischungsverhältnis von 1:1 sowie 1:4 verglichen. Während 1:1-Mischungen lediglich eine co-kristalline Phase, in der Fullerene zwischen den Seitenketten von pBTTT interkalieren, zeigen, resultiert der Überschuss an Fulleren in den 1:4-Proben in der Ausbildung reiner Fullerendomänen zusätzlich zu der co kristallinen Phase. Transiente Absorptionsspektroskopie verdeutlicht, dass Ladungstransferzustände in 1:1-Mischungen hauptsächlich über geminale Rekombination zerfallen, während in 1:4 Mischungen ein beträchtlicher Anteil an Ladungen ihre wechselseitige Coulombanziehung überwinden und freie Ladungsträger bilden kann, die schließlich nicht-geminal rekombinieren.