Free volume of electrospun organic-inorganic copolymers

Basson, Neil (2014-04)

Thesis (MSc)--Stellenbosch University, 2014.

Thesis

ENGLISH ABSTRACT: Two series of amphiphilic, organic-inorganic graft copolymers of poly(methyl methacrylate) and poly(dimethylsiloxane) (PMMA-graft-PDMS), as well as poly(acrylonitrile) and poly(dimethylsiloxane) (PAN-graft-PDMS), were synthesized via conventional free radical copolymerization using the ―grafting through‖ technique. In both series the PDMS macromonomer content varied from 5 wt.% - 25 wt.% and different graft lengths of 1000 g/mol and 5000 g/mol were used. A gradient elution profile was developed to monitor the removal of the unreacted PDMS macromonomer using hexane extraction. In the case of the PAN copolymer series, the gradient profile showed that as the PDMS content in the feed increased, more PAN-graft-PDMS molecules formed relative to homopolymer PAN. In the case of the PMMA copolymer series, mostly PMMA-graft-PDMS molecules were formed as the PDMS content in the feed increased. In the case of the PAN-graft-PDMS series, the PDMS content affected the crystallization behaviour of the PAN segments and lead to a decrease in crystallinity across the composition range as the PDMS content increased. It is shown that the synthesized graft copolymers can be electrospun to produce continuous nanofibers. The effects of polymer solution concentration, copolymer composition and tip-to-collector distance on the fiber morphology are discussed. The rapid stretching of the polymer jet, as well as the rapid solvent evaporation during the electrospinning process, resulted in highly complex nonequilibrium morphologies in the case of the electrospun PAN-graft-PDMS copolymers. The crystallization behaviour of the electrospun fibers of PAN-graft- PDMS was shown to be different from the unprocessed precursor material. Surface oxidised MWCNTs were successfully incorporated and well dispersed into the graft copolymers via the electrospinning process to produce nanocomposite nanofibers. In the case of the PAN-graft-PDMS copolymer series, the presence of MWCNTs in the nanocomposite nanofibers enhanced the overall degree of crystallinity when compared to the unfilled nanofibers. For the first time positron annihilation lifetime spectroscopy (PALS) analysis was performed on the various complex graft copolymer compositions and their electrospun fiber analogues, as well as nanocomposites, to investigate the free volume properties of the various materials. The results revealed that there are two distinct ortho-positronium (o-Ps) lifetime parameters for these complex multiphased materials. The shorter lived lifetime -3 was attributed to the o-Ps annihilation in the amorphous regions of the crystalline PAN phase in the PAN-graft-PDMS copolymer series, as well as to the o-Ps annihilation in the amorphous PMMA phase in the case of the PMMA-graft-PDMS copolymer series. The longer lived lifetime -4 was attributed to the o-Ps annihilation in the more amorphous PDMS phase. In the case of the PMMA series the relative fractional free volume was influenced by the graft lengths, where the 5000 g/mol series showed a larger increase in fractional free volume relative to the shorter 1000 g/mol series. The effects of the tip-to-collector distance during electrospinning, as well as the inclusion of MWCNTs, on the free volume properties are also discussed. It is demonstrated how positron annihilation lifetime spectroscopy can provide valuable and unique information on the internal structure and morphology of the electrospun nanofibers.

AFRIKAANSE OPSOMMING: Twee reekse amfifiliese, organies-anorganiese entkopolimere van poli(metielmetakrilaat) en poli(dimetielsiloksaan) (PMMA-ent-PDMS), asook poli(akrilonitriel) en poli(dimetielsiloksaan) (PAN-ent-PDMS), is gesintetiseer deur konvensionele vrye-radikaalkopolimerisasie. Die PDMS makromonomeerinhoud het gewissel tussen 5 wt.% - 25 wt.% in albei reekse en sykettinglengtes van 1000 g/mol en 5000 g/mol is gebruik. `n Gradient-eluasieprofiel is opgestel om die verwydering van ongereageerde PDMS makromonomeer d.m.v. heksaanekstraksie te monitor. In die PAN kopolimeer reeks het die gradient-eluasieprofiel gewys dat meer PAN-ent- PDMS molekules vorm relatief tot die PAN homopolimeer sodra meer PDMS bygevoeg word. In die PMMA kopolimeer reeks het meer PMMA-ent-PDMS molekules gevorm sodra meer PDMS toegevoeg is. In die geval van die PAN-ent- PDMS reeks, het die PDMS die kristallisasiegedrag van die PAN segmente geaffekteer en `n afname in die totale kristalliniteit veroorsaak soos die PDMS inhoud vermeerder het. Daar word bewys dat die gesintetiseerde entkopolimere geelektrospin kan word om nanovesels te vorm. Die effek van polimeeroplossingskonsentrasie, kopolimeersamestelling en punt-tot-versamelaarafstand op die nanoveselmorfologie word bespreek. Die vinnige strekking van die polimeerjet sowel as die vinnige verdamping van die oplosmiddel gedurende die elektrospinproses het gelei tot hoogs komplekse nie-ekwilibrium morfologieë in die geval van die ge-elektrospinde PAN-ent-PDMS kopolimere. Die kristallisasiegedrag van die nanovesels van PAN-ent-PDMS het verskil van die onverwerkte voorloper materiaal. Oppervlakgeoksideerde MWCNTs is suksevol geïnkorporeer en versprei in die entkopolimere d.m.v. die elektrospinproses om nanosaamgestelde nanovesels te vorm. Die teenwoordigheid van MWCNTs in die nanosaamgestelde nanovesels in die PAN-ent-PDMS kopolimeerreeks het gelei tot `n verbetering in die algehele kristalliniteit in vergelyking met die nanovesels sonder MWCNTs. Positronvernietigingsleeftyd- spektroskopie (PALS) is vir die eerste keer gebruik om die vrye volume van verskillende kompleks entkopolimeersamestellings, hul ge-elektrospinde nanovesels sowel as nanosaamgestelde nanovesels te bestudeer. Die resultate het getoon dat daar twee verskillende orto-positronium (o-Ps) leeftydparameters vir hierdie komplekse multifase materiale bestaan. Die korter leeftydparameter -3 word toegeskryf aan die o-Ps vernietiging in die amorfe areas van die kristallyne PAN fase in die PAN-ent-PDMS kopolimeerreeks, sowel as die o-Ps vernietiging in die amorfe PMMA fase in die PMMA-ent-PDMS kopolimeerreeks. Die langer leeftydparameter -4 word toegeskryf aan die o-Ps vernietiging in die amorfe PDMS fase. Die relatief fraksionele vrye volume van die PMMA reeks is deur die verskillende syketting lengtes beïnvloed. Die 5000 g/mol syketting het `n groter toename in fraksionele vrye volume veroorsaak relatief tot die korter 1000 g/mol syketting. Die effek van die punttot- versamelaar-afstand tydens die elektrospinproses op die vrye volume eienskappe, sowel as die insluiting van MWCNTs, word bespreek. Daar word aangedui hoe positron-vernietigingsleeftyd-spektroskopie waardevolle en unieke inligting kan verskaf oor die interne struktuur en morfologie van die nanovesels.

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