Influence of spatial constraints in non-crystalline regions on the polymer dynamics in semi-crystalline polyethylene: a solid state NMR study

A broad variety of solid state NMR techniques were used to investigate the chain dynamics in several polyethylene (PE) samples, including ultrahigh molecular weight PEs (UHMW-PEs) and low molecular weight PEs (LMW-PEs). Via changing the processing history, i.e. melt/solution crystallization and drawing processes, these samples gain different morphologies, leading to different molecular dynamics. Due to the long chain nature, the molecular dynamics of polyethylene can be distinguished in local fluctuation and long range motion. With the help of NMR these different kinds of molecular dynamics can be monitored separately. In this work the local chain dynamics in non-crystalline regions of polyethylene samples was investigated via measuring 1H-13C heteronuclear dipolar coupling and 13C chemical shift anisotropy (CSA). By analyzing the motionally averaged 1H-13C heteronuclear dipolar coupling and 13C CSA, the information about the local anisotropy and geometry of motion was obtained. Taking advantage of the big difference of the 13C T1 relaxation time in crystalline and non-crystalline regions of PEs, the 1D 13C MAS exchange experiment was used to investigate the cooperative chain motion between these regions. The different chain organizations in non-crystalline regions were used to explain the relationship between the local fluctuation and the long range motion of the samples. In a simple manner the cooperative chain motion between crystalline and non-crystalline regions of PE results in the experimentally observed diffusive behavior of PE chain. The morphological influences on the diffusion motion have been discussed. The morphological factors include lamellar thickness, chain organization in non-crystalline regions and chain entanglements. Thermodynamics of the diffusion motion in melt and solution crystallized UHMW-PEs is discussed, revealing entropy-controlled features of the chain diffusion in PE. This thermodynamic consideration explains the counterintuitive relationship between the local fluctuation and the long range motion of the samples. Using the chain diffusion coefficient, the rates of jump motion in crystals of the melt crystallized PE have been calculated. A concept of "effective" jump motion has been proposed to explain the difference between the values derived from the chain diffusion coefficients and those in literatures. The observations of this thesis give a clear demonstration of the strong relationship between the sample morphology and chain dynamics. The sample morphologies governed by the processing history lead to different spatial constraints for the molecular chains, leading to different features of the local and long range chain dynamics. The knowledge of the morphological influence on the microscopic chain motion has many implications in our understanding of the alpha-relaxation process in PE and the related phenomena such as crystal thickening, drawability of PE, the easy creep of PE fiber, etc.

Soil biogenic emissions of nitric oxide from arid and semi-arid ecosystems

The biogenic production of NO in the soil accounts for between 10% and 40% of the global total. A large degree of the uncertainty in the estimation of the biogenic emissions stems from a shortage of measurements in arid regions, which comprise 40% of the earth’s land surface area. This study examined the emission of NO from three ecosystems in southern Africa which cover an aridity gradient from semi-arid savannas in South Africa to the hyper-arid Namib Desert in Namibia. A laboratory method was used to determine the release of NO as a function of the soil moisture and the soil temperature. Various methods were used to up-scale the net potential NO emissions determined in the laboratory to the vegetation patch, landscape or regional level. The importance of landscape, vegetation and climatic characteristics is emphasized. The first study occurred in a semi-arid savanna region in South Africa, where soils were sampled from 4 landscape positions in the Kruger National Park. The maximum NO emission occurred at soil moisture contents of 10%-20% water filled pore space (WFPS). The highest net potential NO emissions came from the low lying landscape positions, which have the largest nitrogen (N) stocks and the largest input of N. Net potential NO fluxes obtained in the laboratory were converted in field fluxes for the period 2003-2005, for the four landscape positions, using soil moisture and temperature data obtained in situ at the Kruger National Park Flux Tower Site. The NO emissions ranged from 1.5-8.5 kg ha-1 a-1. The field fluxes were up-scaled to a regional basis using geographic information system (GIS) based techniques, this indicated that the highest NO emissions occurred from the Midslope positions due to their large geographical extent in the research area. Total emissions ranged from 20x103 kg in 2004 to 34x103 kg in 2003 for the 56000 ha Skukuza land type. The second study occurred in an arid savanna ecosystem in the Kalahari, Botswana. In this study I collected soils from four differing vegetation patch types including: Pan, Annual Grassland, Perennial Grassland and Bush Encroached patches. The maximum net potential NO fluxes ranged from 0.27 ng m-2 s-1 in the Pan patches to 2.95 ng m-2 s-1 in the Perennial Grassland patches. The net potential NO emissions were up-scaled for the year December 2005-November 2006. This was done using 1) the net potential NO emissions determined in the laboratory, 2) the vegetation patch distribution obtained from LANDSAT NDVI measurements 3) estimated soil moisture contents obtained from ENVISAT ASAR measurements and 4) soil surface temperature measurements using MODIS 8 day land surface temperature measurements. This up-scaling procedure gave NO fluxes which ranged from 1.8 g ha-1 month-1 in the winter months (June and July) to 323 g ha-1 month-1 in the summer months (January-March). Differences occurred between the vegetation patches where the highest NO fluxes occurred in the Perennial Grassland patches and the lowest in the Pan patches. Over the course of the year the mean up-scaled NO emission for the studied region was 0.54 kg ha-1 a-1 and accounts for a loss of approximately 7.4% of the estimated N input to the region. The third study occurred in the hyper-arid Namib Desert in Namibia. Soils were sampled from three ecosystems; Dunes, Gravel Plains and the Riparian zone of the Kuiseb River. The net potential NO flux measured in the laboratory was used to estimate the NO flux for the Namib Desert for 2006 using modelled soil moisture and temperature data from the European Centre for Medium Range Weather Forecasts (ECMWF) operational model on a 36km x 35km spatial resolution. The maximum net potential NO production occurred at low soil moisture contents (<10%WFPS) and the optimal temperature was 25°C in the Dune and Riparian ecosystems and 35°C in the Gravel Plain Ecosystems. The maximum net potential NO fluxes ranged from 3.0 ng m-2 s-1 in the Riparian ecosystem to 6.2 ng m-2 s-1 in the Gravel Plains ecosystem. Up-scaling the net potential NO flux gave NO fluxes of up to 0.062 kg ha-1 a-1 in the Dune ecosystem and 0.544 kg h-1 a-1 in the Gravel Plain ecosystem. From these studies it is shown that NO is emitted ubiquitously from terrestrial ecosystems, as such the NO emission potential from deserts and scrublands should be taken into account in the global NO models. The emission of NO is influenced by various factors such as landscape, vegetation and climate. This study looks at the potential emissions from certain arid and semi-arid environments in southern Africa and other parts of the world and discusses some of the important factors controlling the emission of NO from the soil.

The fabrication and application of semi-crystalline and thermoset-thermoplastic composite colloidal particles with well-defined microstructures

Die Zielsetzung der Arbeit besteht darin, neue Ansätze zur Herstellung strukturierter Kompositpartikel in wässrigem Medium zu entwickeln, welche als die Bildung genau definierter heterogener Strukturen in Kolloidsystemen angesehen werden können. Im Allgemeinen wurden zwei verschiedene Herangehensweisen entwickelt, die sich aufgrund des Ursprungs der gebildeten heterogenen Strukturen unterscheiden: Heterogenität oder Homogenität. Der Erste Ansatz basiert auf der Aggregation heterogener Phasen zur Bildung strukturierter Kolloidpartikel mit Heterogenität in der zugrunde liegenden Chemie, während der Zweite Ansatz auf der Bildung heterogener Phasen in Kolloidpartikeln aus homogenen Mischungen heraus durch kontrollierte Phasenseparation beruht.rnIm Detail beschäftigt sich der erste Teil der Dissertation mit einer neuen Herstellungsmethode für teilkristalline Komposit-Kolloidpartikel mit hoher Stabilität basierend auf der Aggregation flüssiger Monomertropfen an teilkristalline Polyacrylnitrilpartikel. Nach der Aggregation wurden hochstabile Dispersionen bestehend aus strukturierten, teilkristallinen Kompositpartikeln durch freie radikalische Polymerisation erhalten, während ein direktes Mischen der PAN Dispersionen mit Methacrylat-Polymerdispersionen zur unmittelbaren Koagulation führte. In Abhängigkeit von der Glastemperatur des Methacrylatpolymers führt die anschließende freie radikalische Polymerisation zur Bildung von Rasberry oder Kern-Schale Partikeln. Die auf diese Weise hergestellten Partikel sind dazu in der Lage, kontinuierliche Filme mit eingebetteten teilkristallinen Phasen zu bilden, welche als Sauerstoffbarriere Anwendung finden können.rnDer zweite Teil der Dissertation beschreibt eine neue Methode zur Herstellung strukturierter Duroplast-Thermoplast Komposit-Kolloidpartikel. Die Bildung eines Duroplastnetzwerks mit einer thermoplastischen Hülle wurde in zwei Schritten durch verschiedene, separate Polymerisationsmechanismen erreicht: Polyaddition und freie radikalische Polymerisation. Es wurden stabile Miniemulsionen erhalten, welche aus Bisphenol-F basiertem Epoxidharz, Phenalkamin-basiertem Härter und Vinlymonomere bestehen. Sie wurden durch Ultraschall mit nachfolgender Härtung bei verschiedenen Temperaturen als sogenannte Seed-Emulsionen hergestellt. Weitere Vinylmonomere wurden hinzugegeben und nachfolgend polymerisiert, was zur Bildung von Kern-Schale, beziehungsweise Duroplast-Thermoplast Kolloidpartikeln führte. Dabei findet in beiden Fällen zwischen der duroplastischen und der thermoplastischen Phase eine chemisch induzierte Phasenseparation statt, welche essenziell für die Bildung heterogener Strukturen ist. Die auf diese Weise hergestellten Kompositpartikel sind dazu in der Lage, transparente Filme zu bilden, welche unter geeigneten Bedingungen deutlich verbesserte mechanische Eigenschaften im Vergleich zu reinen Duroplastfilmen bereitstellen.rn