Free volume properties of semi-crystalline polymers

Sweed, Muhamed (2011-03)

Thesis (PhD (Chemistry and Polymer Science))--University of Stellenbosch, 2011.

Thesis

ENGLISH ABSTRACT: Positron annihilation lifetime spectroscopy (PALS) is well established as a novel method currently available for the study of polymers at a molecular level because of its sensitivity to the microstructural changes in the polymer matrix. The technique provides unique, but limited, information of the solid state structure – primarily on the nature of the free volume (or unoccupied space) in the polymer due to the less dense packing of polymer chains relative to in other solid materials. In the case of completely homogeneous polymer materials the measurement and interpretation of the positron annihilation parameters is relatively simple. However, in the case of polymers with more complex morphologies the situation becomes less clear. This is due to the possibility of the formation, localization and subsequent annihilation of o-Ps (ortho-positronium) within different areas of the complex morphology. This can result in more than one o-Ps lifetime component being present, and each of the different components corresponds to areas with differing types and amounts of 'open spaces'. In this study a detailed and systematic approach was taken to study the positron annihilation parameters in various semi-crystalline polymers and to correlate these to the chain structure and morphology of the materials. The study focused specifically on polyolefin polymers as these are the most widely used semi-crystalline materials, but more importantly, they offer the possibility to produce a variety of morphological complexity by simple manipulation of the chain structure – while there is essentially no difference in the chemical composition of the materials. The copolymers were selected to study the influence of short-chain branching (amount and length), short-chain branching distribution and tacticity on the morphology, and subsequent positron annihilation lifetime parameters. Three separate topics were addressed. First, preparative temperature rising elution fractionation was used to isolate polymer samples that are homogeneously crystallisable and to produce a series of polymers with differing chain structure and resultant morphologies. Second, additional series were produced by removing specific crystallisable fractions from the bulk materials. Third, the temperature variation of the samples as they approach and go through the crystalline melting point was studied. All the raw positron data were found to be best fitted with a four-component positron annihilation lifetime analysis. The longest lifetime (which is attributed to annihilation of o-Ps in the amorphous phase of the materials) showed systematic variations with the degree and nature of the short-chain branding, tacticity variation, a combination of both short-chain branching and tacticity, and changes in the amorphous phase as a result of heating. The third lifetime component (which is attributed to o-Ps annihilation in or around the crystalline areas of the materials) showed less variation across the sample series. Typically, greater variations were observed in the propylene copolymers than in the ethylene copolymers, which are reflective of the more complex chain structure and corresponding morphology in the propylene copolymer series. Direct evidence for a contribution from the nature of the amorphous phase to the bulk microhardness of the sample was also found.

AFRIKAANSE OPSOMMING: Positronvernietigingsleeftydspektroskopie (PALS) is goed gevestig as ‘n nuwe metode vir die studie van polimere op molekulêrevlak agv die sensitiwiteit van die metode vir mikrostrukturele veranderings in die polimeermatriks. Hierdie tegniek verskaf unieke, maar beperkte, inligting aangaande die vastetoestandstruktuur – veral aangaande die aard van die vryevolume (of onbesette spasie) in die polimeer as gevolg van die minder digte verpakking van polimeerkettings relatief tot in ander vastestowwe. In die geval van volledig homogene polimeriese materiale is die meet en interpretasie van die positronvernietigingsparameters relatief eenvoudig. Maar in die geval van polimere met meer komplekse morfologieë is die situasie minder duidelik. Die rede hiervoor is die moontlikheid vir die formasie, lokalisering en gevolglike vernietiging van o-Ps (orto-positronium) in die verskillende areas van die komplekse morfologie. Dit kan tot gevolg hê dat meer as een o-Ps komponent teenwoordig is en waar elk van die verskillende komponente ooreenstem met areas met verskillende tipes en hoeveelhede 'oop spasies'. In hierdie studie is ‘n sistematiese, in-diepte benadering gebruik om die positronvernietigingsparameters in verskeie semikristallyne polimere te bestudeer en hulle te korreleer met dié van die kettingstruktuur en die morfologieë van die materiale. Hierdie studie het spesifiek gefokus op poliolefiene aangesien hulle die mees algemene semikristallyne materiale is wat gebruik word en, nog meer belangrik, hulle bied die geleentheid om verskeie komplekse morfologieë te lewer dmv eenvoudige manipulasie van die kettingstrukture – terwyl daar basies geen verandering in die chemiesesamestelling van die materiale is nie. Die kopolimere is gekies om die invloed van kort-ketting vertakking (lengte en hoeveelheid), kort-ketting vertakking verspreiding en taktisiteit op die morfologie en vervolgens die positronvernietigingsleeftyd parameters te bestudeer. Drie onderwerpe is aangespreek. Eerstens, preparatiewe temperatuurstygingelueringsfraksionering (prep-TREF) is gebruik om polimeermonsters wat homogeenkristalliseerbaar is te isoleer om sodoende 'n reeks polimere met verskillende kettingstrukture, en gevolglike morfologieë, te lewer. Tweedens, 'n addisionele reekse monsters is berei deur die verwydering van spesifieke kristalliseerbare fraksies vanaf die grootmaatmonsters. Derdens, die temperatuurverandering van die monsters wanneer die monsters naby aan die kristallyne smeltpunt is en wanneer hulle deur die kristallyne smeltpunt gaan is bestudeer. Daar is bevind dat alle rou positrondata ten beste gepas het in 'n vier-komponent positronvernietigingsleeftydanalise. Die langste leeftyd (wat toegeskryf is aan vernietiging van o-Ps in die amorfe fase van die materiaal) het sistematiese variasies getoon met die volgende: hoeveelheid en aard van die kort-kettingvertaking, verandering in taktisiteit, 'n kombinasie van beide kort-kettingvertakking en taktisiteit en veranderings in die amorfiesefase as gevolg van verhitting. Die derde leeftyd komponent (wat toegeskryf is aan die o-Ps vernietiging in of rondom die kristallyne areas van die materiale) het minder variasie in hierdie reeks monsters getoon. Daar is tipies meer variasie waargeneem in die propileenkopolimere as in die etileenkopolimere, wat ’n weerspieëling is van die meer komplekse kettingstruktuur en ooreenstemmende morfologie in die propileenkopolomeerreeks. Direkte bewys vir 'n bydrag van die aard van die amorfe fase tot die grootmaat mikrohardheid van monsters is ook bevind.

Please refer to this item in SUNScholar by using the following persistent URL: http://hdl.handle.net/10019.1/6597
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