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Paper des Monats
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Eingeladener Vortrag
- nein (46)
Chemi- und Thermolumineszenz-Untersuchungen zur Stabilität von Poly(phenyl-p-phenylenvinylen), P-PPV
(1998)
Investigation of Stability of Poly(phenyl-1,4-phenylenevinylene) by Thermo- and Chemiluminescence
(1998)
Stability of poly(phenyl-1,4-phenylene vinylene) investigated by thermo- and chemilumineszenz
(1998)
The thermo-oxidative degradation of a polymeric optical cable is investigated by chemiluminescence, The results are reliable and reproducible. Two distinct processes are reported marked by a peak and a plateau behavior versus the time, respectively. Both processes are ruled by thermally activated processes. Beside the dependencies of temperature and time, the influence of absorbed water is discussed. Chemiluminescence is proposed as a promising candidate for a suitable testing method assessing the thermo-oxidative stability of plastic optical fibers and cables. it requires not more than a simple one-day testing procedure and has the advantage that it can be carried out even within the lo cv temperature ranges of the cables' intended use.
Im Mittelpunkt dieser Arbeit stehen die konjugierten Polymere, die sich durch äußerst interessante elektrooptische Eigenschaften auszeichnen. Die sich daraus ergebenden Anwendungen liegen vor allem auf dem Gebiet der Elektrolumineszenz, z. B. als LED- Materialien. Ein Hauptproblem für die Einsatzfähigkeit ist die Stabilität der konjugierten Polymere. Dabei spielen Oxida-tionsprozesse sowie strukturelle und morphologische Veränderungen eine entscheidende Rolle. Zur Untersuchung der thermooxidativen Stabilität wurde die Chemilumineszenz-Methode (CL) und zum Nachweis der strukturellen und morphologischen Defekte die Thermolumineszenz-Methode (TL) eingesetzt. Um die Stabilität der konjugierten Polymere zu erhöhen, wurden im Rahmen dieser Arbeit zahlreiche Einflussfaktoren auf die thermooxidative Stabilität sowie auf die molekulare Beweglichkeit mit Hilfe der CL und der TL untersucht und diskutiert.
The excitation energy transfer (EET) of a bichromophoric cross-shaped molecule was investigated by stationary polarized fluorescence spectroscopy in the solid state. For this purpose 2,2[prime],7,7[prime]-tetrakis(biphenyl-4-yl)-9,9[prime]-spirobifluorene was embedded in a polymeric bisphenol-A-polycarbonate (PC) matrix. The dependence of the fluorescence on concentration and wavelength was determined. The role of the intermolecular and intramolecular EET is dealt with separately and discussed by means of the degree of polarization. The intermolecular excitation energy transfer is described in terms of a Förster transfer mechanism. The intramolecular transfer is prevented for the zero-point vibrational levels by the molecular cross-shaped structure, but is found for a wide range of wavelength, presumably based on vibrationally excited states.
Degradation effects of automotive coatings after weathering as detected by thermoluminescence
(2004)
Introduction of irregularities into plasma polymers by radiative and auto-oxidative processes
(2005)
Angesichts der spezifischen Bedeutung der Aushärtung von Phenolharzen für ihre Eigenschaften als Ingenieurwerkstoffe besteht großes Interesse an deren quantitativer Charakterisierung. Mittels DSC-Messungen unter hohem Druck (HP-DSC) kann die Vernetzungsreaktion der Phenolharzformmassen durch die Unterdrückung der Verdampfung niedermolekularer Substanzen ohne störende Überlagerungen verfolgt werden. Mittels verschiedener Vernetzungsgrade können die Einflussparameter der Aufheizrate und der Nachtemperung optimiert werden. Die Messergebnisse ermöglichen eine Modellierung der Reaktionskinetik mit dem Ziel einer verbesserten Prozessführung und Qualitätskontrolle in der industriellen Praxis.
Dünne, mit einem gepulsten Plasma hergestellte Polymerschichten wurden untersucht. Diese Plasmapolymere sollten eine chemisch besser definierte Struktur haben, weil der Anteil an rein chemisch polymerisiertem Produkt während der Plasma-aus-Zeit steigen sollte, während der Anteil an Schichtbildung, der innerhalb der kurzen Plasmapulse durch Monomerfragmentierung und statistische Polyrekombination erzeugt wird, zurückgedrängt wird. Der Monomerfragmentierungsprozeß ist im kontinuierlich brennenden Plasma (cw-Mode) demgegenüber der Hauptprozeß. Neben der Anwendung der klassischen Element- und Bindungsanalysentechnik XPS (X-ray Photoelectron Spectroscopy) wurden hier die Schichten auch mittels Thermolumineszenz untersucht. Defekte und Strukturanomalitäten in Polymeren sollten mit dieser Methode charakterisiert werden können. Untersuchungsobjekte waren funktionalgruppentragende Plasmapolymerschichten, die biosensorische oder biokompatible Funktionen besitzen oder als Haftvermittler in Metall-Polymercompositen eingesetzt werden.
Translated Abstract
Characterization of Plasmapolymers by Thermoluminescence
Thin plasma polymer films were deposited using the pulsed plasma (pp) mode. These plasma polymers should possess a more chemically regular structure because of the lower monomer fragmentation during the short plasma pulses and the chemical chain propagation during the plasma-less periods than those produced by the conventional continuous-wave (cw) mode. In addition to the use of the classic thin film characterization method XPS the method of thermoluminescence was applied to characterize defects and structural specifics in the polymer films produced by pp or cw-plasma mode. The thermoluminescence method was applied to functional groups-carrying plasma polymer layers, which are used in medical technology for forming biocompatible and bioactive coatings or in metal-polymer composites as adhesion-promoting interlayers.
Thin plasma polymer films were deposited using the pulsed plasma mode. These plasma polymers should possess a more regular structure than those produced by the conventional continuous-wave (cw) mode, because of lower monomer fragmentation caused by the plasma pulses and the chemical chain propagation during the plasmaless (free!) periods. The thermoluminescence method was applied to functional groups carrying plasma polymer layers which are used in medical technology. Examples are formation of biocompatible, biosensoric and bioactive coatings or in metal polymer composites such as adhesion-promoting interlayers.
In addition to the use of the conventional X-ray Photoelectron Spectroscopy for thin film characterization, the new method of thermoluminescence was applied to characterize undesired defects and structural specifics produced in the polymer films by pp or cw plasma mode. The main areas of focus were oxygen-containing groups produced by post-plasma oxygen introduction via auto-oxidation, oxidation of implemented unsaturations and trapped radical sites known as typical irregular structures in plasma polymers.
Chemiluminescence (CL) is a sensitive method of investigating the thermo-oxidative stability of polymers in the early stages of degradation. Therefore, CL measurements were applied to different automotive coatings to evaluate their degradation behavior during artificial weathering. In this work, CL measurements were carried out for different automotive coatings to follow their degradation behavior during artificial weathering. The CL emission depends on sample-specific parameters like stabilizer, matrix, or hardener; experimental parameters like the oxygen partial pressure; and exposure parameters like the duration of weathering. The potential of CL could be demonstrated by classifying materials into categories of good, medium, and low degradation performance at a much earlier stage of weathering exposure than in combination with the usual visual detection of weathering effects.
Thermally stimulated luminescence (TL) can be used to detect damage in the early stages of degradation after artificial weathering, and to analyze the efficiency of stabilizers used in automotive coatings. TL is particularly suitable for this task due to its inherent high sensitivity to structural, morphological, and chemical changes in macromolecular chains. In this work, TL measurements were carried out for different automotive coatings to follow their degradation progression during artificial weathering. The TL results demonstrate high sensitivity to parameters like stabilizers, matrices, hardeners, and weathering time, and provide an opportunity to monitor the early stages of damage in polymers, which therefore reduce the time required for further outdoor weathering tests.