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The melting behavior of polymers can provide information on their crystallization mechanism. However, the origin of the time-dependent low endotherm, or annealing peak, and the extent of melting-recrystallization-remelting during heating are still debated. The crystallization and subsequent melting behavior of isotactic polystyrene are explored in the context of Stroblâ "s 3-Phase model using differential scanning calorimetry (DSC), small angle X-ray scattering (SAXS), and wide angle X-ray diffraction. DSC experiments confirm the existence of a crystallization time-dependent low endotherm, and melting-recrystallization-remelting processes during heating. SAXS analysis using the correlation function confirms that the lamellar thickness increases with crystallization temperature and is independent of time. The spread between equilibrium melting and crystallization temperatures determined in this work (Tfâ"" = 533K, Tcâ"" = 544K) is much smaller than reported by Strobl et al. (Tfâ"" = 562K, Tcâ"" = 598K). These differences are partially attributed to overestimation in lamellar thicknesses calculated through the interface distribution function. Analysis of diffraction broadening shows that the apparent crystal size decreases with crystallization time, suggesting the formation of smaller/less perfect crystals during secondary crystallization. These results are consistent with observations that the glass transition temperature increases with crystallization time and supports the idea that secondary crystallization leads to increased amorphous conformational constraints. These results also suggest that the upward shift of the annealing peak during secondary crystallization is associated with increased amorphous constraints rather than increased crystal dimensions. The lack of distinction between Tfâ"" and Tcâ"" and the evolution of crystal size during crystallization stand in direct contrast with Stroblâ "s model. / Master of Science

Polímeros híbridos são caracterizados por conter numa mesma partícula dois tipos diferentes de polímero, normalmente incompatíveis e ligados por ligações covalentes. Neste trabalho, a síntese de um polímero híbrido acrílico-alquídico pelo processo de miniemulsão foi investigada. Com o objetivo de compreender como diferentes variáveis na fórmula afetam as características físico-químicas finais do látex, um planejamento experimental foi desenhado com o auxílio do software DX9 e os resultados analisados por modelos empíricos de superfície de resposta. Os fatores variados (variáveis independentes) foram: quantidade de co-estabilizante, surfactante e iniciador. Cada um dos fatores contribuiu para a alteração de pelo menos uma característica avaliada, e a sinergia entre eles afeta diretamente o teor de RDG, resposta indicativa do grau de grafitização entre as espécies. O coestabilizante contribuiu para o aumento do diâmetro médio de gotas e da polidispersidade de tamanho de partículas, enquanto reduziu a dureza do filme. A concentração de surfactante alterou o número de partículas por litro, reduzindo o diâmetro médio de partículas e aumentando a polidispersidade. O iniciador aumentou a conversão monomérica. Todas as dispersões de polímero híbrido produzidas apresentaram redução do tamanho médio de gotas para partículas, indicando evidência de nucleação secundária. As avaliações por microscopia eletrônica de transmissão (TEM) e microscopia de força atômica (AFM) mostraram que a morfologia obtida é do tipo núcleo-casca. / Hybrid polymers are defined by the presence of two or more different kinds of polymers in the same particle, typically incompatible and linked by covalent bonds. In this work, the synthesis of an alkyd-acrylic hybrid polymer produced by miniemulsion polymerization has been investigated. With the goal of understanding how different variables in the recipe affect the final characteristics of the latex, a design of experiment was planned using DX9 software and the results were analyzed by response surface methodology. The factors studied (independent variables) were: amount of co-stabilizer, surfactant and initiator. Each of these factors contributed to change at least one of the evaluated characteristics, and the synergy between them directly affects the RDG content, response of the polymer degree of grafting. Costabilizer contributed to increase the average droplets diameter and polydispersity of particle size, while reducing the film hardness. The amount of surfactant changed the number of particles, reducing the average particle size and increasing polydispersity. Initiator increased the monomer conversion. All hybrids dispersions presented a decrease in the droplet size to particle size, indicating evidence of secondary nucleation. Core-shell morphology was observed through transmission electron microscopy (TEM) and atomic force microscopy (AFM).

Polímeros híbridos são caracterizados por conter numa mesma partícula dois tipos diferentes de polímero, normalmente incompatíveis e ligados por ligações covalentes. Neste trabalho, a síntese de um polímero híbrido acrílico-alquídico pelo processo de miniemulsão foi investigada. Com o objetivo de compreender como diferentes variáveis na fórmula afetam as características físico-químicas finais do látex, um planejamento experimental foi desenhado com o auxílio do software DX9 e os resultados analisados por modelos empíricos de superfície de resposta. Os fatores variados (variáveis independentes) foram: quantidade de co-estabilizante, surfactante e iniciador. Cada um dos fatores contribuiu para a alteração de pelo menos uma característica avaliada, e a sinergia entre eles afeta diretamente o teor de RDG, resposta indicativa do grau de grafitização entre as espécies. O coestabilizante contribuiu para o aumento do diâmetro médio de gotas e da polidispersidade de tamanho de partículas, enquanto reduziu a dureza do filme. A concentração de surfactante alterou o número de partículas por litro, reduzindo o diâmetro médio de partículas e aumentando a polidispersidade. O iniciador aumentou a conversão monomérica. Todas as dispersões de polímero híbrido produzidas apresentaram redução do tamanho médio de gotas para partículas, indicando evidência de nucleação secundária. As avaliações por microscopia eletrônica de transmissão (TEM) e microscopia de força atômica (AFM) mostraram que a morfologia obtida é do tipo núcleo-casca. / Hybrid polymers are defined by the presence of two or more different kinds of polymers in the same particle, typically incompatible and linked by covalent bonds. In this work, the synthesis of an alkyd-acrylic hybrid polymer produced by miniemulsion polymerization has been investigated. With the goal of understanding how different variables in the recipe affect the final characteristics of the latex, a design of experiment was planned using DX9 software and the results were analyzed by response surface methodology. The factors studied (independent variables) were: amount of co-stabilizer, surfactant and initiator. Each of these factors contributed to change at least one of the evaluated characteristics, and the synergy between them directly affects the RDG content, response of the polymer degree of grafting. Costabilizer contributed to increase the average droplets diameter and polydispersity of particle size, while reducing the film hardness. The amount of surfactant changed the number of particles, reducing the average particle size and increasing polydispersity. Initiator increased the monomer conversion. All hybrids dispersions presented a decrease in the droplet size to particle size, indicating evidence of secondary nucleation. Core-shell morphology was observed through transmission electron microscopy (TEM) and atomic force microscopy (AFM).

The crystallization and melting behaviors of an ethylene/1-hexene copolymer and series of narrow molecular weight linear polyethylene and poly(ethylene oxide) fractions were studied using a combination of ultra-fast and conventional differential scanning calorimetry, optical microscopy, small angle X-ray scattering, and wide angle X-ray diffraction. In the case of linear polyethylene and poly(ethylene oxide), the zero-entropy production melting temperatures of initial lamellae of isothermally crystallized fractions were analyzed in the context of the non-linear Hoffman-Weeks method. Using the Huggins equation, limiting equilibrium melting temperatures of 141.4 ± 0.8oC and 81.4 ± 1.0oC were estimated for linear polyethylene and poly(ethylene oxide), respectively. The former and the latter are about 4oC lower and 12.5oC higher than these predicted by Flory/Vrij and Buckley/Kovacs, respectively. Accuracy of the non-linear Hoffman-Weeks method was also examined using initial lamellar thickness literature data for a linear polyethylene fraction at different crystallization temperatures. The equilibrium melting temperature obtained by the Gibbs-Thomson approach and the C2 value extracted from the initial lamellar thickness vs. reciprocal of undercooling plot were similar within the limits of experimental error to those obtained here through the non-linear Hoffman-Weeks method. In the next step, the Lauritzen-Hoffman (LH) secondary nucleation theory was modified to account for the effect of stem length fluctuations, tilt angle of the crystallized stems, and temperature dependence of the lateral surface free energy. Analysis of spherulite growth rate and wide angle X-ray diffraction data for 26 linear polyethylene and 5 poly(ethylene oxide) fractions revealed that the undercooling at the regime I/II transition, the equilibrium fold surface free energy, the strength of the stem length fluctuations and the substrate length at the regime I/II transition are independent of chain length. The value of the equilibrium fold surface free energy derived from crystal growth rate data using the modified Lauritzen-Hoffman theory matches that calculated from lamellar thickness and melting data through the Gibbs-Thomson equation for both linear polyethylene and poly(ethylene oxide). Larger spherulitic growth rates for linear polyethylene than for poly(ethylene oxide) at low undercooling is explained by the higher secondary nucleation constant of poly(ethylene oxide). While the apparent friction coefficient of a crystallizing linear polyethylene chain is 2 to 8 times higher than that of a chain undergoing reptation in the melt state, the apparent friction coefficient of a crystallizing poly(ethylene oxide) chain is about two orders of magnitude lower. This observation suggests that segmental mobility on the crystal phase plays a significant role in the crystal growth process. In case of the statistical ethylene/1-hexene copolymer, the fold surface free energies of the copolymer lamellae at the time of crystallization and melting increase with increasing undercooling, approaching the same magnitude at high undercooling. As a result of this temperature dependence, the experimental melting vs. crystallization temperature plot is parallel to the Tm = Tc line and the corresponding Gibbs-Thomson plot is non-linear. This behavior is attributed to the fact that longer ethylene sequences form a chain-folded structure with lower concentration of branch points on the lamellar surface at lower undercooling, while shorter ethylene sequences form lamellar structures at higher undercooling exhibiting a higher concentration of branch points on the lamellar surface. Branch points limit the ability of lamellar structures to relax their kinetic stem-length fluctuations during heating prior to melting. / Ph. D. / Morphology of semi-crystalline polymers is strongly affected by their crystallization conditions. Thermodynamic and kinetic models allow us to understand the crystallization mechanism of a semi-crystalline polymer and relate its crystallization conditions to the final morphology. In this research, we studied the molar mass dependence of the crystallization and melting behaviors of narrow molecular weight distribution linear polyethylene (LPE) and poly(ethylene oxide) (PEO) fractions using a modified Lauritzen-Hoffman (LH) secondary nucleation theory. We have shown that the equilibrium melting temperature of LPE and PEO fractions found from the non-linear Hoffman-Weeks method are within the experimental uncertainty identical with these measured directly for extended chain crystals or derived from a Gibbs-Thomson analysis. The value of the equilibrium fold surface free energy derived from crystal growth rate data using the modified LH theory matches that calculated from lamellar thickness and melting data through the Gibbs-Thomson equation for both LPE and PEO. We reported that the higher segmental mobility of PEO in the crystalline phase leads to significantly lower apparent chain friction coefficients during crystal growth compared to LPE. We also studied the role of short-chain branching in the crystal growth kinetics of ethylene/1-hexene copolymers. We observed that the fold surface free energies during crystallization and during melting are both function of the undercooling while the ratio of the former to the latter decreases with increasing undercooling. We proposed that this behavior may be related to the concentration of short-chain branches at the surface of the lamellae, where higher concentration leads to lower relaxation.