The high demand on accuracy in radiotherapy is to a large extent ensured through measurements of dose to water. The liquid ionisation chamber (LIC) is a type of detector that has several desirable properties for such measurements, e.g. a small active volume and minimal directional dependent response. There are, however, still gaps in knowledge concerning fundamental characteristics of this kind of detector. One of these characteristics is the detector’s response variation in relation to water with varying beam quality. This work aims to increase the knowledge of the LIC’s behaviour and attempts to come up with a method to construct correction factors for the response variation. The response model proposed by Eklund and Ahnesjö [2009] has been evaluated for two LICs, one filled with isooctane and the other with tetramethylsilane (TMS). The evaluation was done for two photon beams, 6 and 15 MV. It was found that the energy dependent response calculations from this method could not explain the difference between the LIC and reference air-filled ionisation chamber measurements in the larger fields. The response model leads to corrections for the TMS filled LIC in the direction away from the reference measurements. For the LIC filled with isooctane the corrections points towards the reference but were too small to completely explain the difference. / De höga kraven på noggrannhet i radioterapi kontrolleras genom mätningar av dos till vatten. Vätskejonisationskammaren (LIC) är en detektor med flera önskvärda egenskaper för sådana mätningar, den har exempelvis en liten aktiv volym och en respons med litet vinkelberoende. Fortfarande finns luckor i kunskapen om denna detektors grundläggande egenskaper. En av dessa är hur detektorns respons skiljer sig från vatten beroende på strålkvalitet. Syftet med detta arbete har varit att öka kunskapen om LICens beteende samt att försöka komma fram till en metod för att konstruera korrektionsfaktorer för den strålkvalitetsberoende responsen. Responsmodellen, presenterad av Eklund och Ahnesjö [2009], utvärderades för två LICar, en fylld med isooktan och en med tetrametylsilan (TMS), i två fotonstrålar, 6 och 15 MV. Den energiberoende responsen som beräknades från responsmodellen kunde inte förklara skillnaden mellan LIC- och referenskammarmätningarna i de stora fälten. Som referenskammare användes en luftfylld jonkammare. Modellen ledde till korrektioner i riktning bort från referenskammarvärdet för den TMS-fyllda kammaren. För kammaren med isooktan skedde korrektionen i riktning mot referenskammaren men var för liten för att helt förklara skillnaden.

Dissertation--Mathematisch-naturwissenschaftliche Fakultät--Zürich Universität, 2000. / Bibliogr. p. 98-104.

Thèse de doctorat : Physique : Metz : 1999. / Thèse soutenue sur ensemble de travaux. Bibliogr. p. 140.

Reproduction de : Thèse doctorat : Chimie-physique : Metz : 2002. / Titre provenant de l'écran-titre. Notes bibliographiques.

No description available.

The present study employs a range of soft-ionisation mass spectrometry techniques to study the degradation of model compounds of poly(methyl methacrylate), poly(n-butyl acrylate) and poly(2-hydroxyethyl methacrylate) under conditions designed to simulate the worst-case scenario that would be experienced by a polymer used in a surface coating on a steel roof. Vinyl-terminated and saturated polymers were degraded for periods of up to 2 years under simulated solar radiation at a temperature of 95??C, temperature of 95 ??C in the dark, and simulated solar radiation at 35??C. Similar degradation mechanisms were observed under heat and UV radiation. The presence of UV radiation accelerated the degradation occurring at high temperature, and vice versa. The combination of heat and UV radiation is far more detrimental to the polymers than either of these conditions alone. Both vinyl-terminated and saturated pMMA degraded under UV radiation at 95??C, whereas under conditions of UV radiation alone or high temperature alone, the saturated polymer was found to be stable. The vinyl-terminated pMMA degrades in all cases via the formation of ethylene oXide-type end groups, which subsequently rearrange under the expulsion of formaldehyde and 2-oxo-propionic acid methyl ester. This is in contrast to all previous literature, in which pMMA degrades via depolymerisation and is stable at 95??C. Degradation of pBA included a degradation mechanism similar to that of pMMA in addition to other polymer fragments, some of which cannot be assigned. pBA (both saturated and vinyl-terminated) showed a tendency to crosslink under all degradation conditions in this study. Only saturated pHEMA was stable under thermal degradation. In all other cases, pHEMA showed some degradation, but displayed a much greater tendency to crosslink rapidly. Terminal vinyl bonds were shown in all cases to be a weak point in the polymer with respect to degradation. pMMA was found to be the least reactive of these polymers. pHEMA showed some small degradation but had a greater tendency to crosslink via the hydroxyethyl side groups. pBA does not have any such reactive groups, and its crosslinking reaction may be explained via the acrylate backbone, or the longer alkyl ester group.

Contemporary mass spectrometry (MS) instrumentation featuring electrospray ionisation (ESI) or matrix-assisted laser desorption/ionisation (MALDI) ion sources were used to characterise the polymer distributions generated in various free radical polymerisations, allowing insights to be gained into the reaction mechanisms operating in these systems. In studying atom transfer radical polymerisation (ATRP) mediated star polymerisations of methyl acrylate (MA), ESI was found to be more effective in obtaining a comprehensive list of the distinct products present in the samples under investigation when compared to the employed MALDI technique. Furthermore, these studies showed that terminal Br losses observed at relatively high monomer to polymer conversions could be accounted for via mechanisms involving the acetone derived radicals (CH3)2??OH, ??H3 and ??H2COCH3. Through the use of ESI, it was found that for bulk polymerisations of MA and aqueous media polymerisations of N-isopropylacrylamide (NIPAAm) initiated using 60Co ??-irradiation and mediated via reversible addition-fragmentation chain transfer (RAFT), hydrogen radicals formed via the radiolysis of RAFT agent and/or monomer, and in the case of the NIPAAm system, water, are capable of initiating the polymerisations. In the NIPAAm polymerisations under scrutiny, it was also observed that hydroxyl radicals generated via the radiolysis of water may contribute towards the initiation process, and that propagating chains can potentially become terminated via trithiocarbonate cleavage reactions. By using ESI instruments to characterise oligomer samples produced via the free radical polymerisations of vinyl phosphonates, it was observed that chain propagations are initiated via activated monomer radicals, which likely form as a result of transfer reactions involving initiator fragments and vinyl phosphonate monomer units. Transfer to monomer reactions were suggested to limit chain growth in these systems, and evidence was also found for scission reactions involving alkoxy moieties which are formed via intramolecular methine carbon abstraction reactions. Characterisation of the polymer distributions generated in R-group approach RAFT MA star polymerisations using an ESI instrument allowed formation processes operating in acrylate star living/controlled radical polymerisations (CRPs) to be ascertained. Initiator fragment derived linear chains, ideal stars, star-star couples, and terminated star products formed as a result of disproportionation and combination reactions were detected. Evidence for mid-chain radical (MCR) derived reaction pathways was also observed; specifically, for termination reactions involving intermolecularly formed MCRs on both star arms and linear chains, and for re-propagation of intermolecularly formed MCRs on star arms.

Thesis (Ph. D.)--University of Chicago. / Also available on the Internet.

Tübingen, Univ., Diss., 2005.

Universiẗat, Diss., 2001--München.