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The dissertation describes and assembles the building blocks for sound and accurate models for solid-state polymerization process systems of condensation polymers, particularly poly(ethylene terephthalate) and nylon-6. The work centers on an approach for modeling commercial-scale, as opposed to laboratory-scale, systems. The focus is not solely on coupled polymerization and diffusion, but extends to crystallization, physical properties, and phase equilibrium, which all enhance the robustness of the complete model. There are three applications demonstrating the utility of the model for a variety of real, industrial plant operations. One of the validated simulation models is for commercial production of three different grades of solid-state PET. There are also validated simulation models for the industrial leaching and solid-state polymerization of nylon-6 covering a range of operating conditions. The results of these studies justify our mixing-cell modeling approach as well as the inclusion of all relevant fundamental concepts. The first several chapters discuss in detail the engineering fundamentals that we must consider for modeling these polymerization process systems. These include physical properties, phase equilibrium, crystallization, diffusion, polymerization, and additional modeling considerations. The last two chapters cover the modeling applications. / Ph. D.

Two novel classes of siloxane containing, organic-inorganic block copolymers were prepared using different synthetic approaches. The first copolymers were alternating poly(arylene ether phosphine oxide)-poly(dimethylsiloxane) systems, prepared via oligomeric silylamine-hydroxyl reactions. Secondly, segmented nylon 6,6-poly(dimethylsiloxane) block copolymers were synthesized via a non-aqueous adaptation of the "nylon 6,6 salt" hydrolytic polyamidization, using bis(aminopropyl) dimethylsiloxane oligomer as a co-reactant. Three series of "perfectly" alternating block copolymers were produced from well characterized hydroxyl-terminated poly(arylene ether phosphine oxide) and dimethylamine-terminated poly(dimethylsiloxane) oligomers, in order to investigate both block length and chemical composition effects. Copolymerization in chlorobenzene resulted in high molecular weight materials capable of forming optically clear, nanophase separated films, which displayed unusual morphologies and good mechanical strength. Thermal gravimetric analysis showed high thermo-oxidative stability and increasing char yield with increasing siloxane content. Additional thermal and mechanical investigations provided evidence of selective phase mixing, particularly at shorter block lengths. Surface analysis showed an enrichment of the siloxane blocks at the air-polymer interface in comparison to the bulk state. This behavior increased in proportion to the length of the parent siloxane oligomers. Evaluation of selected optical properties, e.g., refractive indices, revealed linear trends resulting in values of compositionally weighted averages. Conversely, a series of nylon 6,6-siloxane copolymers were produced from the polycondensation of preformed propylamine-terminated poly(dimethylsiloxane)s, solid nylon 6,6 salt and a corresponding amount of adipic acid to afford siloxane-amide semi-crystalline copolymers with siloxane content ranging from 10 to ~45 wt%. The characterization of high molecular weight and covalent siloxane-amide linkages was hindered by insolubility. For example, crystallinity of the nylon 6,6 precluded the use of common solution techniques, while the susceptibility of the siloxane blocks towards ionic redistribution prevented the use of strongly acidic solvents. However, development of a novel analytical technique using solid state 13C NMR and liquid-solid extraction provided evidence for the presence of covalent bonding between the dissimilar oligomer chains. Thermal gravimetric analysis of resultant copolymers revealed an increase in char yield with increasing siloxane content, a preliminary indicator of increased fire resistance, which was supported by subsequent qualitative Bunsen burner observations. Differential scanning calorimetry showed retention of the polyamide crystalline melt with levels of siloxane incorporation of up to 45 weight %. In conclusion, two novel classes of polydimethylsiloxane containing block copolymers have been successfully synthesized, despite the complications created as a result of the polar/non-polar interactions developed between a semi-inorganic polydimethylsiloxane and the hydrocarbon based polyarylene ethers and nylon 6,6. / Ph. D.

This thesis presents a multiscale model of an industrial nylon-6 leacher. We develop several models at various spatial scales and implement them together in a simplistic, efficient way to develop an overall leacher model. We solve dynamic transport differential equations using the finite-volume method and method of lines in an in-house-developed FORTRAN program. We use the ODEPACK package of ordinary differential equation (ODE) solvers to solve our system of coupled ODEs. Our multiscale model performs transport, thermodynamic, physical property, and mass-transfer calculations at a finite-volume scale. We introduce two additional scales: a mesoscale, in which we perform computational fluid dynamic (CFD) simulations, and a molecular scale. Our CFD simulations solve for turbulent properties of fluid flowing over a packed bed. We incorporate the turbulent diffusivity of the fluid into our finite-volume leacher model. We perform molecular simulations and use the conductor-like screening model-segment activity coefficient (COSMO-SAC) model to generate solubility predictions of small, cyclic oligomers in water and ε-caprolactam. Additionally, we develop an extension of COSMO-SAC to model polymer species, which we refer to as Polymer-COSMO-SAC, and apply it to solve liquid-liquid equilibrium equations. We present a unique methodology to apply COSMO-based models to polymer species, which shows reasonable results for nylon-6. Because of the computational intensity of our Polymer-COSMO-SAC liquid-liquid equilibrium algorithm, we generate pre-computed tables of equilibrium predictions that we may import into our leacher model. Our integration of multiscale models maximizes efficiency and feasibility with accuracy. We are able to use our multiscale models to estimate necessary parameters, but we need to fit two mass-transfer related parameters to industrial data. We validate our model against the plant data and find average-absolute errors in the final mass percent of ε-caprolactam and cyclic dimer in polymer chips of 25.0% and 54.7%, respectively. Several plant data sets are suspected outliers and we believe an unforeseen equilibrium limitation may cause this discrepancy. If we remove these outlying data sets, we then find average-absolute errors of 7.5% and 19.3% for ε-caprolactam and cyclic dimer, respectively. We then use our validated model to perform application and sensitivity studies to gain critical insight into the leacher's operating conditions. / Master of Science

This thesis was made in cooperation with Roxtec. Roxtec specialises in cable sealingsolutions and are world leading in their area. In many of Roxtec’s products steel isused in the frame holding the sealing rubber. To lower Roxtec’s environmental foot-print plastic would be used instead in the frames if possible, more specific polyamide6.6 with 25% glass fiber reinforcement (PA66GF25). Polyamide is affected to agreater extent by temperature and humidity than steel and therefore poses a greaterrisk when considering the sealing capability in harsh conditions. The purpose of thisthesis is therefore to investigate the effects on the Young’s modulus by temperatureand relative humidity, which both correlate to moisture content in the plastic. Theintended temperature and moisture saturation interval are -40◦C to 80◦C and 0% to100% moisture saturation respectively. Tensile test samples were made through machining samples from existing productsand conditioning them to desired moisture content. With the use of tensile testingthe Young’s modulus could be determined for a number of combinations of temper-ature and moisture content. From this data an approximated polynomial surfaceof the Young’s modulus could be produced. The conditioning of the test piecescould be accelerated by submersion in heated water, decreasing conditioning timeto less than two days. The approximation of the Young’s modulus function couldbe done using polynomial approximation. The resulting polynomial for the positivetemperatures was of the third order dependant of the two variables moisture con-tent and temperature. For the negative temperatures a single variable polynomialwas approximated due to only one moisture content being tested for. To ensure thevalidity of the model each test combination consisted of three individual tensile testof which an average was calculated. The approximated function was then comparedto a data sheet value for a certain moisture content and temperature. From theresulting surface approximation of the Young’s modulus in positive temperatures itcan be deduced that PA66GF25 is more greatly affected by moisture content thantemperature. Especially at low levels of moisture content where the rise in Young’smodulus is exponential while more linear at higher moisture contents. The maximumand minimum Young’s modulus was found to be 8 GPa and 2.7 GPa respectively.The negative temperature approximation was restricted to one moisture content andtherefore resulted in a graph. The behaviour of this graph was likely a result of icein the material as similarities to a study regarding the mechanical properties of icewas found. / Detta examensarbete gjordes i sammarbete med Roxtec. Roxtec specialialiserar sig ikabeltätningslösningar och är världsledande i området. I många av Roxtecs produk-ter så används stål till att försegla gummi. För att minska Roxtecs miljöpåverkan såskulle plast användas till tätningarnas ramar om möjligt, speficikt polyamid 6.6 med25% glasfiberförstärkning (PA66GF25). Polyamid påverkas till större andel av tem-peratur och luftfuktighet än stål och utsätts därmed för en större risk med avseendepå tätnings kapabiliteten i tuffa miljöer. Syftet med detta arbete är därmed attundersöka effekterna på Elasticitetsmodul från temperatur och luftfuktighet, vilkakorrelerar mot fuktmättnadsgraden i plasten. Det avsedda temperaturintervallet är-40◦C till 80◦C och 0% till 100% fuktmättnadsgrad. Dragprovstesterna gjordes genom bearbetning av existerande produkter följt av kon-ditionering till önskad fuktmättnadsgrad. Genom genomförandet av dragprov, såkunde Youngs modul bestämmas för ett antal kombinationer av temperaturer ochfukterhalter. Från denna data så kunde en polynomyta för Youngs modul approx-imeras. Konditioneringen av dragprovsbitarna kunde accelereras genom nedsänkningi upphettat vatten, vilket minskade konditioneringstiden till mindre än två dygn. Ap-proximeringen av funktionen för Youngs modul kunde göras genom polynomapprox-imering, vilket resulterade i en tredje ordnings polynom beroende på två variablernafuktmättnadsgrad och temperatur. En annan approximation gjordes för de nega-tiva temperaturerna, då enbart temperaturberoende beteende undersöktes med enkonstant fuktmättnadsgrad. För att säkerställa validiteten av modellen så gjordestre mätningar på varje testkombination ifrån vilket ett medel kalkylerades. Den ap-proximerade funktionen jämfördes sedan med värdena från datablad för en viss fukt-mättnadsgrad och temperatur. Från den resulterande ytapproximationen av Youngsmodul för de positiva temperaturerna, så kan slutsatsen att PA66GF25 är avsevärtmycket mer påverkad av fukt än temperatur dras. Detta är tydligare för de testernamed låga fuktmättnadsgrader då ökningen av Youngs modul är exponentiell medanden är mer linjär för högre fuktmättnadsgrad. Den maximala och minimala Youngsmodul visade sig vara 8 GPa och 2.7 GPa respektive. De negativa temperaturernasapproximation var begränsad till en fuktmättnadsgrad och därmed resulterade i engraf kring 5 GPa. Beteendet hos denna graf var troligtvis ett resultat från isen imaterialet vars beteende är snarlikt en studie på isens mekaniska egenskaper visadepå.

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No laboratório de Análise, Processamento e Reologia de Materiais Poliméricos da Escola Politécnica da USP tem sido estudadas blendas de Poliamida-6 (PA-6) e filme de poli(vinil butiral) (PVB), como uma alternativa para reciclagem do filme de PVB oriundo do processo de separação dos componentes do vidro laminado pós-consumo. As propriedades mecânicas de uma blenda polimérica dependem da sua morfologia e, por sua vez, a morfologia depende das propriedades reológicas e da tensão interfacial entre os polímeros formadores da blenda, que para o caso de blendas envolvendo filme de PVB podem mudar em função da concentração de plastificante presente na composição do filme. Apesar da importância do seu conhecimento, a tensão interfacial entre PA-6 e filme de PVB não é conhecida. O presente trabalho teve como objetivo avaliar a tensão superficial do filme de PVB e da PA-6. O método utilizado foi o da gota pendente. Também estudou-se a influência da adição de plastificante na tensão superficial do filme de PVB. Os resultados mostraram que a tensão superficial dos polímeros estudados decresce com o aumento da temperatura (temperatura variando entre 240 e 260ºC). Em particular, para o filme de PVB a entropia de superfície ( (d/dT) ) apresentou um valor acima dos normalmente encontrados para polímeros fundidos. Este comportamento foi atribuído à estabilidade térmica do filme. O filme de PVB utilizado nos ensaios de tensão superficial foi caracterizado por Espectroscopia no Infravermelho (FTIR), Espectroscopia no Ultravioleta/Visível (UV-VIS), Espectroscopia Eletrônica para Análise Química (ESCA) e Análise Termogravimétrica (TG). Os resultados obtidos comprovaram que há mudanças na estrutura do PVB durante sua exposição a temperaturas elevadas, por longo período de tempo (condições do ensaio de tensão superficial). Foi observado, primeiramente, a evaporação do plastificante, seguida por perda de grupos polares (-OH, C=O e C-O-C) presentes na estrutura do PVB. A tensão superficial da Poliamida-6 foi determinada para temperaturas de 250 e 260ºC. Os resultados mostraram que a PA-6 manteve-se estável durante os ensaios. / In the Rheology and Polymer Processing Laboratory of Escola Politécnica of the University of São Paulo, Polyamide-6 / poly(vinyl butiral) film blends have been studied as an alternative for the recycling of post-consumption laminated glasses. The mechanical properties of these blends were studied and explained in light of their morphology. The morphology of polymer blends strongly depends on the rheological behavior of the blend and on the interfacial tension between the polymers forming the blend. In the case of Poliamide-6 (PA-6)/poly(vinyl butiral) (PVB) film blends, the interfacial tension depends on the plasticizer concentration present in PVB film. However, to our knowledge neither the PA-6/PVB film interfacial tension nor the surface tension of PVB film at temperatures above softening temperatures have been evaluated. In this work, the surface tension of poly(vinyl butyral) and polyamide was evaluated using the pendant drop method. Also it was tried to evaluate the surface tension of PVB film as a function of plasticizer content. The surface tension values obtained were in the same range as the ones obtained for other molten polymers: the surface tension decreases with increasing temperature (for temperatures ranging from 240 to 260°C). However, the value of PVB film surface entropy ((d/dT) where is the surface tension and T is the temperature) was much larger than values reported for other molten polymers. This result was attributed to thermal stability of PVB film during the surface tension measurement. The drops of PVB film after surface tension analysis were examined for any change in their functional groups using infrared spectroscopy (FITIR), ultraviolet-visible spectroscopy (UV/VIS), electron spectroscopy for chemical analysis (XPS/ESCA) and thermogravimetric analysis (TG). The results showed that changes in the chemical structure of PVB film occur during surface tension measurement. First, the plasticizer within the PVB film evaporates and, then, the PVB suffers reduction of polar units and creation of C=C bonds. The surface tension of PA-6 was evaluated for temperatures of 250 and 260°C. The PA-6 remained stable during tests.