The objective of this research was to develop an in-situ sensing technique that monitors the molecular-level response of ions and dipoles to an applied electric field in order to characterize the changes in state of a polymer resin during chemical processing. This technique needs to be capable of monitoring the reaction progress not only in the laboratory setting but also in-situ in the processing tool or reaction environment. Frequency Dependent Electromagnetic Sensing (FDEMS) was selected for this task.;This dissertation investigates the applicability of FDEMS to monitoring two types of processing methods: reactive and batch reactor. The reactive processing system examined involves the processing of a high glass transition thermoplastic, either polyethylene ether or polyether imide blended with a thermoset, diglycidyl ether of bisphenol-A and 4,4'-methylene bis (3-chloro 2,6-diethylaniline]. The batch reactor processing systems examined involve the in-situ process control of an industrial batch reactor process involving five different systems: epoxy acrylic, polyester, latex, emulsion for lotions and surfactants.

The rheological and structural properties of polymeric liquids cannot be condensed within a single numerical model. They should be described within hierarchical, multi-level numerical models in which each sub-model is responsible for different time and length scales; atomistic, mesoscopic, and continuum. In this study, the rheological and structural properties of linear, short-chain polyethylene liquids were investigated from the classical atomistic level to the mesoscopic and continuum levels of description. At the atomistic level of description, nonequilibrium molecular dynamics (NEMD) simulations of linear, short-chain polyethylene liquids spanning from C16H24 to C128H256 were performed to advance our knowledge of fundamental characteristic of chain molecules under shear and planar elongational flow. Furthermore, entanglement characteristics, such as the shortest primitive path length, and the network configurations, were investigated as functions of strain rate in both vastly different flow fields using the topological Z-code. At the mesoscopic level of description, Brownian dynamics (BD) simulations of a freely-jointed chain with equivalent contour length to C78H158 were carried out to compare single-chain dynamics in dense liquids (NEMD) and dilute solutions (BD) under shear flow. In addition, the macromolecular configurational diversity of individual chains in dense liquids and dilute solutions was explored using a brightness distribution method inspired by the rheo-optical investigation of DNA solutions. Based on these observations, a simple coarse-grained mesoscopic model for unentangled polymeric liquids and semi-dilute solutions was proposed and compared with NEMD simulation data and experiments of semi-dilute DNA solutions under shear flow in terms of the rheological and structural properties, such as viscosity, normal stress coefficients, conformation tensor, and so on. Moreover, this model was further coarse-grained to the continuum level through pre-averaging and compared with NEMD simulation data to examine the relationships between different levels of description on the rheological and structural properties of unentangled polymeric materials under shear flow.

No description available.

The goal of this research was to develop a controllable process to convert a thermoplastic powder-coated carbon-fiber towpreg into uniform and consolidated ribbon. The approach comprised four primary activities. (1) The patent and processing literature was studied to evaluate the state of the art. (2) A functional ribbon fabrication technique was developed by scaling-up, in a novel configuration, hardware components found in the literature. (3) The ex parte ribbonizing process was characterized by calibrating equipment, determining steady state and studying cause and effect between process parameters and ribbon quality. (4) Process design and control methods were derived from heat transfer and pulling force analyses. The ex parte ribbonizer process comprises a material handling system, a preheat region, a heated stationary bar assembly, and a cooled nip roller assembly. Appropriate timing of important contacts is key to fabricating quality ribbon. Process characterization and analyses revealed key flow mechanisms. Ribbon microstructure changes most at the bars. Ribbon macrostructure changes most at the nip. An isothermal bar contact is a practical processing constraint for ensuring uniform squeeze flow bar spreading. All bar drag force is attributed to shear stress in the interfacial viscous boundary layer between the towpreg and the stationary bar surface. Continually sensing pulling force is a good indication of process control. The research goal was achieved because the ex parte ribbonizer can be used to convert polymer powder towpreg into uniform and fully-consolidated ribbon in a controllable manner.

Fibers in biological scaffolds like fibronectin stiffen when they experience forces between cells. It will expose binding sites under contractile forces and then form disulfide bonds. This on-demand strain-stiffening is a desirable property in synthetic materials. Tran et.al. (2017) mimicked the “cryptic” design of fibronectin by copolymerizing thiol crosslinking sites with monomers containing poly (ethylene glycol) chains. When the PEG chain increased from 350 to 950 g/mol, the strains-stiffening became on-demand while the curing process extended from 3 hours to 15 hours. Extra steric hindrance brought by longer PEG chains caused decreasing mass transfer rates of cryptic sites while the same level of strain rate was introduced. I proposed to use stronger ultrasound mechanical perturbation so that higher strain rate can be induced, and the shielding effect brought by the PEG chain can be overcome more easily. Utilizing ultrasound as a stimuli has the potential to improve the gelation speed or achieve high mechanical performance while retain the long shelf life of the “cryptic” materials. To test this hypothesis, I synthesized “cryptic” polymer with aceto-acetoxy and primary amine as crosslinking sites such that, the only time limiting step is brought by the long PEG chain. This is because the bond formation reaction between these two reactive groups is rapid and spontaneous. When switching from weak to strong mechanical perturbation, the change in gelation speed owing to accelerated mass transfer between crosslinking sites can be easily compared. When the PEG chain is 300 Mw and 30 mol % crosslinking sites density, this “cryptic” polymer only showed strain-stiffening under ultrasound while strain under a rheometer was not able to overcome steric hindrance. Signs of chain scission appeared when the ultrasound amplitude was set at 75 %, but was counteracted by reducing amplitude mode over the time. The crosslinking was optimized by varying the ultrasound amplitude and intensity and a final mode of 1 hour 75 % amplitude, 0.5 hour 50 % amplitude and 3.5 hours 25% amplitude provided greatly improved on demand crosslinking. The estimated kinetic constant using this mode was two times higher than that of under simple shear strain. Through this study, I found that ultrasound can improve the curing time of this “cryptic” polymer system since it induces higher strain rate and expedite the mass transfer rate between crosslinking sites and optimizing the ultrasonic amplitude profile to limit chain scission provides improved crosslinking performance.

<p>This thesis contains two parts. The first involves the theoretical modelling of bulk, thermal, homo- and copolymerizations of styrene with another vinyl monomer in continuous flow stirred tank and tubular reactors. The second involves an experimental study of such polymer production in pilot plant scale reactors. Kinetic modelling fundamentals, applicable assumptions and their implications are discussed. Three series of experimental runs were performed in a 1.4 liter stirred tank reactor. The experimental conditions were in the range of 200 to 300 C with residence times of 15- 60</p> <p>minutes. The first set was done with pure styrene to verify the current styrene kinetic model and provide more detail on the formation of oligomers. Two additional series of experiments were performed with two different comonomer compositions. The monomers were styrene and acrylic acid. Parameter estimation and model verification were attempted with all data. The parameter estimation results are necessarily uncertain due to the low number of experiments possible with pilot plant work and the low variance of the responses obtained in experimentation on high temperature systems. The kinetic mechanism initiation, oligomer formation supported in this work describing styrene thermal and polymer production are Trimer formation is suppressed in the copolymerization of styrene with acrylic acid. This is due to the reaction of acrylic acid monomer with the thermal initiation intermediate, thus preventing rearrangement to trimer species.</p> <p>Trimer formation is accelerated by the addition of chlorine radical to the reaction. This radical reacts with the intermediate to produce chlorinated trimer species and prevents macroradical formation. The addition of a tubular reactor was found to severely increase polymer oil fraction and decrease molecular weight, with only a minor productivity increase.</p> <p>It is believed thermal degradation is <em>very </em> significant in determining molecular weights at temperatures greater than 280 c.</p> / Master of Engineering (ME)

Master of Science / Glass has long been used in glazing applications because of its transparency, stiffness, hardness, resistance to corrosion, and recyclability. Despite these useful features, however, glass is a very brittle material, lacking the ability to usefully absorb energy. Multi-material laminates have been produced as an alternative for glazing applications to improve energy absorption and other functionality requirements. As the demand for these laminates has increased in the construction, automotive, and defense sectors, a need for a more durable system has become apparent. One such example is the laminated glass systems often used in automobiles where two sheets are bonded (laminated) together with a plastic interlayer. Several types of interlayers have been used for these laminated systems, with polyvinyl butyral (PVB) being the most prevalent. A more recently developed interlayer type is thermoplastic polyurethane (TPU), which has the ability to bond to substrates other than glass, making it useful for applications like ballistic-resistant glass laminates, which often involve sheets made of polycarbonate. This study aims to explore the durability of laminated polycarbonate systems by investigating the interaction of environment and TPU viscoelastic behavior on the time-dependent crack growth in these laminates. The main test utilized is the wedge test, where a wedge is inserted between two polycarbonate adherends bonded together with an interlayer. The wedge causes a debond (a crack) to form. This crack may then grow over time. The crack growth in wedge test specimens with different TPUs is evaluated at various temperature and humidity conditions. A separate test, referred to as dynamic mechanical analysis (DMA), is conducted to determine the thermomechanical properties of the TPUs. These properties are then used to analyze the results of the wedge tests. In addition to different TPU types, the effects of edge seals and surface treatment to improve bonding are compared. Models are used to analyze the resulting data to support the prediction of lifetimes of laminated polycarbonate systems employing the TPUs investigated.

Thesis (MSc (Chemistry and Polymer Science))--University of Stellenbosch, 2005. / Polymerization using the reversible addition-fragmentation chain transfer (RAFT) process affords a researcher control over the molecular weight and polydispersity of the final polymer. Research is being carried out globally, using heterogeneous RAFT systems, as these systems offer superior industrial possibilities. Many emulsion systems fail when incorporating RAFT agents due to phase separation and colloidal instability. Exchanging conventional emulsion polymerizations with predispersed polymerization systems (i.e. miniemulsions) has shown many improvements. Evidence of uncontrolled aqueous phase polymerization (i.e. not mediated by the RAFT process) has however been found. This behaviour is similar to polymerization in a conventional emulsion polymerization system, but is not expected in miniemulsion polymerization.

Thesis (MSc)--University of Stellenbosch, 2005. / ENGLISH ABSTRACT: Chemical and molecular tagging agents have illustrated their diversity in a number of different applications. One of the most significant applications includes the use of chemical tagging agents for product registration in industry. Industrial enterprises producing good products need to ensure product authenticity to prevent duplication through piracy and unscrupulous industrialists. Fluorescent probes are chemical compounds that satisfy most of the technical and commercial aspects that are required to be excellent tagging agents. They are generally quick to synthesize, do not affect the product integrity, display little or no impact on the uses of the product or the environment and they can be identified by relatively simple detection procedures. The aim of the present study was to synthesize fluorescent polymers as tagging agents for the paint industry. 7-Hydroxy-2H-chromen-2-one (A1) and 7-hydroxy-4-methyl-2H-chromen-2-one (B1), commercially available fluorescent hydroxyl compounds, were selected as the starting materials. An esterification reaction resulted in the production of 2-oxo-2H-chromen-7-yl acrylate (A2) and 4-methyl-2-oxo-2H-chromen-7-yl acrylate (B2), which are acrylic-type monomers that were required for polymerisation. Studies showed that fluorescence was maintained during the esterification. Copolymers poly(MMA-co-A2), poly(MMA-co-B2), poly(BA-co-A2) and poly(BA-co-B2), synthesized via homogeneous free radical initiated copolymerisation, revealed how copolymer compositions were affected by the feed compositions and the pattern of monomer incorporation over time. This was investigated by following individual monomer consumption rates by 1H-NMR spectroscopy. Fluorescence studies revealed that the fluorescence behaviour of A2 and B2 was maintained during the copolymerisation. Latex particles, with fluorescent behaviour, were synthesized via in situ miniemulsion polymerisation. High molecular weight copolymers with monodisperse particle sizes (nm range) were obtained. A bench-top UV lamp and UV-reflectance studies confirmed the fact that fluorescent latex particles can be identified and quantified respectively, when dispersed in paints that are either free of titanium dioxide or paints that contain titanium dioxide. / AFRIKAANSE OPSOMMING: Die diversiteit van chemiese en molekulêre merkers in ‘n verskeidenheid van toepassings is al telkemale geïllustreer. Een van die mees belangrike toepassings in die industrie is die gebruik van chemiese merkers vir produkregistrasie. Industrieë wat goeie produkte verskaf moet die egtheid van hul produkte kan verseker deur duplikasie via nadruk (Eng: piracy) deur ander te voorkom. Fluoresserende merkers is chemiese stowwe wat aan die meeste van die tegniese en kommersiële vereistes voldoen om as uitstekende merkers te dien. Die sintese van die merkers is gewoonlik nie tydrowend nie, beïnvloed nie die integriteit van die produk nie, het min of geen impak op die gebruike van die produk of die omgewing en kan deur relatief eenvoudige prosedures bepaal word. Die doel van hierdie studie was die sintese van fluoresserendepolimere om as merkers in die verfindustrie te dien. 7-Hidroksie-2H-chromen-2-oon (A1) en 7-hidroksie-4-metiel-2H-chromen-2-oon (B1), fluoresserende hidroksielverbindings wat kommersieël beskikbaar is, is gekies as uitgangstowwe vir die bereiding van die merkers in hierdie studie. ‘n Esterifikasie-reaksie het gelei tot die produksie van 2-okso-2H-chromen-7-ielakrilaat (A2) en 4-metiel-2-okso- 2H-chromen-7-ielakrilaat (B2). Hierdie produkte is tipiese akrilaat-tipe monomere wat benodig word vir polimerisasie. Ondersoeke het getoon dat fluoressensie behoue tydens esterifikasie gebly het. Die kopolimere poli(MMA-ko-A2), poli(MMA-ko-B2), poli(BA-ko-A2) en poli(BA-ko-B2) is deur homogene vry-radikaal-geïnisieerde kopolimerisasie gesintetiseer. Daar is vasgestel hoe die kopolimeersamestelling geaffekteer is deur die samestelling van die reagense (Eng: feed composition) en die patroon van monomeer inkorporasie met tyd. Dit was ondersoek deur die tempo van verbruik van die individuele monomere d.m.v. 1H-KMR spektroskopie te bepaal. Daar is verder vasgestel dat die fluoressensie van A2 en B2 gedurende kopolimerisasie behoue gebly het. Latekspartikels, met fluoressensie gedrag, is via in-situ mini-emulsie-polimerisasie gesintetiseer. Hoë molekulêre massa kopolimere met monodisperse partikelgroottes (in die order van nanometers) is verkry. Deur van ‘n UV-lamp en UV-refleksie studies gebruik te maak is daar bepaal dat fluoresserende latekspartikels in polimere, in verf - wat of titaniumdioksied bevat of geen titaniumdioksied bevat nie -, beide geïdentifiseer and gekwantifiseer kan word.

Thesis (MSc)--University of Stellenbosch, 2007. / ENGLISH ABSTRACT: The main objective of this project was the controlled synthesis of graft copolymers via a thiol-ene addition mechanism. The Reversible Addition-Fragmentation chain Transfer (RAFT) process was used in all polymerization reactions with the aim to achieve a certain degree of control over the molecular weight. Several synthetic steps were required in order to obtain the final graft copolymer and each step was investigated in detail. Firstly, two RAFT agents (cyanovaleric acid dithiobenzoate and dodecyl isobutyric acid trithiocarbonate) were synthesized to be used in the various polymerization reactions of styrene and butyl acrylate. This was done successfully and the RAFT agents were used to synthesize low molecular weight polystyrene branches of the graft copolymer. Different molecular weights were targeted. It was found that some retardation phenomena were present especially at high RAFT agent concentrations. The polystyrene branches that were synthesized contained RAFT end-groups. Various pathways were explored to modify these RAFT end-groups to form thiol end-groups to be used in the thiol-ene addition reaction during the grafting process. The use of sodium methoxide for this purpose proved most successful and no evidence of the formation of disulfide bridges due to the initially formed thiols was detected. Allyl methacrylate (AMA) was chosen as monomer to be used for the synthesis of the polymer backbone because it has two double bonds with different reactivities. For the first time, RAFT was used to polymerize AMA via the more reactive double bond to obtain linear poly(allyl methacrylate) (PAMA) chains with pendant double bonds. However, at higher conversions, gelation occurred and the molecular weight distributions were uncontrolled. NMR was successfully used to study the tacticity parameters of the final polymer. Finally, the synthesis of the graft copolymer, PAMA-g-polystyrene, was carried out by means of the “grafting onto” approach. The thiol-functionalized polystyrene branches were covalently attached to the pendant double bonds of the PAMA polymer backbone via a thiol-ene addition mechanism in the presence of a free radical initiator. A Multi- Angle Laser Light Scattering (MALLS) detector was utilized in conjunction with Size- Exclusion Chromatography (SEC) to obtain molecular weight data of the graft copolymer. The percentage grafting, as determined by 1H-NMR, was low. / AFRIKAANSE OPSOMMING: Die hoofdoel van hierdie projek is die beheerde sintese van ‘n entkopolimeer via ‘n merkaptaan-een addisiereaksie. Die sogenaamde “Reversible Addition-Fragmentation chain Transfer” (RAFT) proses is in al die polimerisasiereaksies gebruik met die doel om ‘n mate van beheer oor die molekulêre massa van die polimere te verkry. Verskeie stappe (waarvan elkeen ten volle ondersoek is) was nodig om die finale entkopolimeer te verkry. Eerstens is twee RAFT-agente (sianovaleriaansuur ditiobensoaat en dodekielisobottersuur tritiokarbonaat) gesintetiseer vir gebruik in verskeie polimerisasiereaksies van stireen en butielakrilaat. Hierdie stap was suksesvol en die RAFT-agente is toe gebruik vir die sintese van lae molekulêre massa polistireensytakke vir die entkopolimeer. Die molekulêre massas van die sytakke is gevarieer en daar is gevind dat vertragings in die polimerisasiereaksies voorgekom het, veral by hoë konsentrasies van die RAFT-agente. Die polistireensytakke wat gemaak is, besit almal ‘n RAFT-eindgroep. Verskeie roetes is bestudeer ten einde die RAFT-eindgroepe tot merkaptaan-eindgroepe te modifiseer om sodoende tydens ‘n merkaptaan-een addisiereaksie gebruik te word. Die gebruik van natriummetoksied was hier die suksesvolste en daar was geen teken van die vorming van disulfiedbrûe as gevolg van die oorspronklik gevormde merkaptane nie. Allielmetakrilaat (AMA) is gekies as die monomeer wat gebruik sou word vir die sintese van die polimeerruggraat omdat die monomeer twee dubbelbindings met verskillende reaktiwiteite besit het. Vir die eerste keer is RAFT gebruik vir die polimerisasie van AMA via die meer reaktiewe dubbelbinding om lineêre poli(allielmetakrilaat) (PAMA) kettings met dubbelbindings in die sygroepe te verkry. Gelvorming en onbeheerde molekulêre massaverspreiding het egter by hoër monomeeromsettings voorgekom. KMR is susksekvol gebruik om die taktisiteitsparameters van die finale polimeer te bestudeer. Ten slotte is die sintese van die entkopolimeer, PAMA-g-polistireen, uitgevoer deur die aanhegting van voorafgevormde sytakke. Die polistireensytakke met die merkaptaaneindgroepe is kovalent geheg aan die dubbelbindings in die sygroepe van die PAMA-polimeerruggraat via ‘n merkaptaan-een addisiemeganisme in die teenwoordigheid van ‘n vrye radikaalinisieerder. ‘n Kombinasie van gelpermeasiechromatografie en multi-hoeklaserligverstrooiing is gebruik om die molekulêre massa van die entkopolimeer te bepaal. Die persentasie sytakke soos bepaal deur 1H-KMR was laag.