The objectives of this study are to synthesize poly(dimethylsilane) (PDMS) preceramic polymer and to investigate its effect on morphology, flame retardant and mechanical properties of polypropylene (PP) based composites. There are mainly two parts in this thesis. In the first part, PDMS was synthesized by electrochemical polymerization of dichlorodimethylsilane, which was dissolved in 1,2 dimethoxyethane (DME) solvent consisting of tetrabutyl ammonium perchlorate (TBAP), as supporting electrolyte. PDMS was obtained in powder form and characterized with Fourier transform infrared, ultraviolet-visible and proton nuclear magnetic resonance spectroscopic analyses, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Since PDMS has some impurities coming from TBAP and DME, alternatively, the PDMS synthesis was done by electrochemical reduction of dichlorodimethylsilane without using solvent and/or supporting electrolyte for seven days. PDMS was produced as pure and characterized with the same methods used for previous synthesis. In the second part of this thesis, PP based composites with additives were prepared by using a twin-screw extruder and injection molding machine and were characterized with limiting oxygen index (LOI), horizontal burning, TGA, differential scanning calorimetry (DSC), tensile and impact tests and SEM analysis. Triphenyl phosphate, boron phosphate, magnesium hydroxide, intumescent flame retardants (IFR) (melamine phosphate (MP) and pentaerythritol (PER)), antimony trioxide and poly(methylsilsesquioxane) were additives used in this study other than PDMS. According to LOI test results, the highest LOI value among the PDMS composites was obtained in 1% PDMS, 14.25% MP and 4.75% PER (w/w) containing composite as 24%, whereas the LOI value of neat PP was measured as 17.5%. It was determined that elastic moduli of all the composites studied were higher than neat PP.

Dendrimerai tai naujai dendritinių polimerų klasei priskiriamos makromolekulės. Jų dydis, funkcinių grupių skaičius yra tiksliai apibrėžti ir gali būti kontroliuojami sintezės metu. Dėl išskirtinių struktūrinių savybių, dendrimerai jau keletą dešimtmečių yra intensyviai tyrinėjamos medžiagos. Pagrindinis disertacijos tikslas yra ištirti PPI ir PAMAM dendrimerų, funkcionalizuotų CAzPA ir ESA fotochrominiais junginiais optines savybes bei šviesa inicijuotų fotocheminių reakcijų dinamiką panaudojus kelias tyrimų metodikas. Kadangi CAzPA ir ESA junginių fotochromizmas yra susijęs su šviesa indukuota izomerizacijos bei tautomerizacijos fotocheminėmis reakcijomis, todėl darbe buvo siekiama ištirti šiais junginiais funkcionalizuotų dendrimerų dinaminių savybių priklausomybę nuo dendrimero tipo bei jo generacijos. Ištyrus PPI ir PAMAM dendrimerų funkcionalizuotų CAzPA junginiais plėvelių ir tirpalų dinamines savybes, buvo nustatyta, kad izomerizacijos sparta nepriklauso nuo dendrimero tipo, tirpiklio ir žadinančios spinduliuotės energijos. Dendrimerų plėvelių sužadintos būsenos relaksacijos trukmė yra apie 15 ps, o tai apie 7 kartus lėčiau nei tirpaluose. Eksperimentiškai ir teoriškai ištyrus skirtingų generacijų PPI dendrimerų funkcionalizuotų ESA fotochrominiais junginiais optines savybes, buvo nustatytos keturios stabilios ESA funkcinių grupių tautomerinės formos, kurių pagrindinės būsenos energijos yra skirtingos. Skirtingų dendrimero generacijų sužadintos būsenos dinamikos... [toliau žr. visą tekstą] / Dendrimers are multivalent, well-defined materials that constitute a new class of polymer macromolecules. They have been extensively studied over the past several decades mainly due to their exceptional structure properties. The size of molecule, number of terminal groups, molecular weight and several other properties of dendrimers could be precisely controlled during synthesis. The main goal of this thesis is to investigate the optical properties and light induced photochemical reaction dynamics within the PPI and PAMAM dendrimers functionalized by CAzPA and ESA type terminal groups by means of several spectroscopic techniques. Because photochromism of CAzPA and ESA type terminal groups is associated with light induced isomerization and tautomerization photochemical reactions, the main attention of present thesis was devoted to investigate dynamical properties of functionalized dendrimers as an influence of dendrimer type and its generation. Investigations of dynamic properties of PPI and PAMAM dendrimers functionalized with the CAzPA terminal groups have shown that isomerization rate is insensitive to dendrimer type, solvent and excitation wavelength. The isomerization rate of the dendrimer films take place in about 15 ps and it is only seven times slower than in dendrimer solvent. Both experimental and theoretical optical studies performed on PPI dendrimers functionalized with the ESA type terminal groups reveal four stable tautomeric forms with different energy in the... [to full text]

Dendrimers are multivalent, well-defined materials that constitute a new class of polymer macromolecules. They have been extensively studied over the past several decades mainly due to their exceptional structure properties. The size of molecule, number of terminal groups, molecular weight and several other properties of dendrimers could be precisely controlled during synthesis. The main goal of this thesis is to investigate the optical properties and light induced photochemical reaction dynamics within the PPI and PAMAM dendrimers functionalized by CAzPA and ESA type terminal groups by means of several spectroscopic techniques. Because photochromism of CAzPA and ESA type terminal groups is associated with light induced isomerization and tautomerization photochemical reactions, the main attention of present thesis was devoted to investigate dynamical properties of functionalized dendrimers as an influence of dendrimer type and its generation. Investigations of dynamic properties of PPI and PAMAM dendrimers functionalized with the CAzPA terminal groups have shown that isomerization rate is insensitive to dendrimer type, solvent and excitation wavelength. The isomerization rate of the dendrimer films take place in about 15 ps and it is only seven times slower than in dendrimer solvent. Both experimental and theoretical optical studies performed on PPI dendrimers functionalized with the ESA type terminal groups reveal four stable tautomeric forms with different energy in the... [to full text] / Dendrimerai tai naujai dendritinių polimerų klasei priskiriamos makromolekulės. Jų dydis, funkcinių grupių skaičius yra tiksliai apibrėžti ir gali būti kontroliuojami sintezės metu. Dėl išskirtinių struktūrinių savybių, dendrimerai jau keletą dešimtmečių yra intensyviai tiriamos medžiagos. Pagrindinis disertacijos tikslas yra ištirti PPI ir PAMAM dendrimerų, funkcionalizuotų CAzPA ir ESA fotochrominiais junginiais optines savybes bei šviesa inicijuotų fotocheminių reakcijų dinamiką panaudojus kelias tyrimų metodikas. Kadangi CAzPA ir ESA junginių fotochromizmas yra susijęs su šviesa indukuota izomerizacijos bei tautomerizacijos fotocheminėmis reakcijomis, todėl darbe buvo siekiama ištirti šiais junginiais funkcionalizuotų dendrimerų dinaminių savybių priklausomybę nuo dendrimero tipo bei jo generacijos. Ištyrus PPI ir PAMAM dendrimerų funkcionalizuotų CAzPA junginiais plėvelių ir tirpalų dinamines savybes, buvo nustatyta, kad izomerizacijos sparta nepriklauso nuo dendrimero tipo, tirpiklio ir žadinančios spinduliuotės energijos. Dendrimerų plėvelių sužadintos būsenos relaksacijos trukmė yra apie 15 ps, o tai apie 7 kartus lėčiau nei tirpaluose. Eksperimentiškai ir teoriškai ištyrus skirtingų generacijų PPI dendrimerų funkcionalizuotų ESA fotochrominiais junginiais optines savybes, buvo nustatytos keturios stabilios ESA funkcinių grupių tautomerinės formos, kurių pagrindinės būsenos energijos yra skirtingos. Skirtingų dendrimero generacijų sužadintos būsenos dinamikos... [toliau žr. visą tekstą]

This dissertation discusses the polymorphism, crystallization and melting behavior of propylene-ethylene random copolymers. It also discusses the results of studies of the miscibility and the competitive liquid-liquid demixing and crystallization processes in blends of poly(propylene) and poly(1-butene). In the first part of this study, polymorphism of propylene-ethylene copolymers is studied by wide angle X-ray diffraction. By comparing the a and y crystal phase contents in samples with different ethylene content as well as samples isothermally crystallized at different temperatures, it was shown that increasing ethylene content as well as increasing crystallization temperature promotes the formation of the y-phase. Comparison of the results from fractionated samples and unfractionated samples with similar ethylene contents reveals that in propylene-ethylene copolymers with similar micro-structure, the polymorphism, crystallization and melting behavior are mainly determined by their ethylene content. The issue of co-unit inclusion and its effect on crystallization and melting behavior are also discussed. In the second part of this dissertation, the miscibility behavior of atactic - poly(propylene) (at-PP) and atactic poly(1-butene) (ai-P1B) with different molecular weights is investigated by differential scanning calorimetry. The phase diagram of at-PP and at-P1B blend of molecular weight (87K/48.5K) shows a upper critical solution temperature (UCST) behavior. The UCST behavior is consistent with predictions by the group contribution method. Miscibility behavior of high molecular weight isotactic poly(propylene) (it-PP) and isotactic poly(1-butene) (it-P1B) blend is investigated by a combination of optical microscopy and scanning electron microscopy, differential scanning calorimetry and dynamic mechanical analysis. These studies reveal that for the molecular weights investigated, it-PP and it-P1B form blends that are partially miscible in the liquid state. Liquid-liquid demixing is observed by optical microscopy at temperatures above the melting temperature of the it-PP component and is also inferred from scanning electron micrographs of the freeze fracture surface of quenched blends after extraction of the it- P1B component with cyclohexane. It-PP spherulites grow through both liquid phases at relative rates that depend markedly on the crystallization temperature. The complex multiple-melting behavior of the it-PP component in the blend is explained in terms of a bimodal distribution of it-PP lamellar crystals which result from crystal growth in the phase-separated liquid. Finally, the dynamic mechanical analysis data are explained in terms of a liquid-liquid demixing process that results in a significant degree of phase mixing. / Ph. D.

Superparamagnetic nanoparticles have potential applications in targeted drug delivery and as magnetic resonance imaging contrast agents. Magnetite clusters are of particular interest for these applications because they provide higher magnetic flux (under a magnetic field) than individual magnetite nanoparticles, are biocompatible, and their size and compositions can be controlled. This thesis involves the controlled synthesis and characterization of clusters composed of magnetite nanoparticles stabilized with an amphiphilic block copolymer. It outlines a method to design and form well-defined and colloidally stable magnetite clusters. A Multi Inlet Vortex mixer (MIVM) was used because it is a continuous process that yields particles with relatively narrow and controlled size distributions. In the MIVM, four liquid streams collide under turbulent conditions in the mixing chamber where clusters form within milliseconds. The formation of magnetite clusters was studied in the presence of amphiphilic block copolymers containing poly (ethylene oxide) to provide steric stabilization and control of size distributions using flash nanoprecipitation. First, the mixer was tested using β-carotene as a model compound to form nanoparticles stabilized with an amphiphilic triblock copolymer poly(propylene oxide)-b-poly(ethylene oxide) (F127) at different Reynolds numbers and supersaturation values. Size analysis was done using dynamic light scattering and nanoparticle tracking analysis techniques. The cluster structure was studied using electron microscopy and magnetite compositions were measured using thermogravimetric analysis. Finally, the stability of magnetite clusters was studied over time and the effect of an applied magnetite field on the colloidal stability was investigated. / Master of Science

Copolymers that contain terminal or pendent functional groups have great potential in the biomedical area due to their biocompatibility and tunable properties.1-3 In this research, two vinyl functional epoxides, vinyldimethylsilylpropyl glycidyl ether (VSiGE) and ethoxy vinyl glycidyl ether (EVGE), were synthesized. These heterobifunctional monomers were polymerizable via the epoxide groups and can be functionalized via thiol-ene reactions through the pendent vinyl groups. A series of amphiphilic block copolyethers based on poly(ethylene oxide) and poly(1,2-butylene oxide) that incorporate VSiGE or EVGE were synthesized and characterized. The vinyl ether and vinyl silane functional groups were functionalized after polymerization and the functional polymers formed pH-sensitive micelles in aqueous medium. The copolyethers were loaded with ritonavir yielding well-controlled nanoparticles. Poly(L-glutamic acid) is comprised of naturally occurring L-glutamic acid repeating units that are linked together with amide bonds. In this research, we have prepared magnetic block ionomer complexes based on poly(ethylene oxide)-b-poly(L-glutamic acid) copolymers. This is of interest due to the biocompatibility and biodegradable nature of the poly(L-glutamic acid) component of the backbone. Allyl- and thiol-functional poly(ethylene oxide)-b-poly(L-glutamic acid) copolymers were also synthesized and coated onto the surface of iron oxide nanoparticles. Allyl- and thiol-tipped single particles were reacted with each other to prepare magnetic clusters. Transverse relaxivities of the clusters were found to be significantly higher than that of single particles. One major problem in commercial development of therapeutic proteins is their poor transport across cellular membranes and biological barriers such as the blood-brain barrier (BBB). One solution to this problem is to modify proteins with amphiphilic block copolymers such as PEO-b-PPO-b-PEO, Pluronics®. However, it isn't possible to independently tune the two PEO block lengths with commercial Pluronics® since a difunctional PPO macroinitator is utilized to grow both PEO blocks simultaneously (HO-EOn-b-POm-b-EOn-OH). Another challenge is introducing functional group which allows post-polymerization functionalization for specific applications. In this study, a series of heterobifunctional asymmetric amino-EOn1-b-POm-b-EOn2-OH block copolymers (APs) with different molecular weights of each block were synthesized and the amino terminal group was conjugated to an antioxidant enzyme, Cu/Zn superoxide dismutase (SOD1). The conjugates were characterized and their cellular uptake was investigated. / Ph. D.

Integrally moulded hinges and tension bands are important features in packaging components for plastic closures and their function is critically dependent on the flow induced micromorphology in the hinge section. Polymer characteristics and processing of the hinge also have an influence on the hinge properties obtained. This study is aimed at obtaining interrelationships between polymer characteristics, in-cavity flow, microstructure development and hinge properties, to produce hinges with enhanced functional properties. Three different virgin polypropylene (PP) grades were investigated (homopolymer PP-H, random copolymer PP-RC and impact copolymer PP-IC) and injection moulding simulation was carried out using Moldflow software. In-cavity data acquisition has been carried out for different sets of injection moulding conditions, using high performance transducers and a data acquisition system. A comparison between Moldflow simulation and practical injection moulding data suggests that, for thin wall injection moulded components the real time pressure data are in close agreement during the injection stage. During the packing stage there is some disagreement between these data, since the thickness of hinge and tension band sections are 0.4 mm and 0.5 mm respectively, suggesting that these dimensions are extending the capability of the software. An extensive study using a design of experiments (DoE) approach was carried out on both practical and predictive data. Injection velocity and melt temperature were the most influential factors on the component mechanical properties. From the optical micrographs it is observed that PP-RC has a finer micro-structure compared to PP-H and PP-IC and some micrographs confirm Moldflow simulation results in which hesitation effects are evident, as the flow converges into the thin hinge and tension band sections. PP-clay nanocomposites (PP-CN) were prepared using a twin screw compounder. Transmission electron microscopy (TEM) has shown some evidence of dispersion and exfoliation of the clay particles in the PP matrix. However, X-ray diffraction (XRD) results show a reduction in inter-layer spacing of PPCN s possibly due to clay compaction. The addition of nano-clay however has not resulted in any significant improvements in the mechanical properties of hinges and tension bands. The high degree of molecular orientation induced in the hinge and tension-band sections appears to mask any improvements attributed to the addition of nano-clay. From the reprocessed and post consumer recyclate (PCR) study conducted on hinges and tension bands, it is seen that with an increase in both the re-processing and PCR content there is a decrease in the component strength of around 14%, giving scope to potentially use PCR in future packaging applications. Investigations conducted on colour pigments (violet and green) reveal that the onset of crystallisation for green pigmented mouldings is considerably higher (16°C) than for natural and violet mouldings. Optical micrographs also reveal a finer microstructural texture for green components, indicating a high nucleating capability of the green pigment. Irrespective of the colour, both for hinges and tension bands, the yield stress values were around twice as high as the values quoted in the manufacturer s data sheet for isotropic PP, due to the high levels of molecular orientation in the hinge and tension band sections. In order to industrially validate the findings from the DoE study, commercial closures were produced in industry on a production tool then characterised. In the case of tension bands, there was a good agreement between the results obtained from lab scale and industrial study due to the relatively simple geometry. For hinges this agreement is not so clear. Finally a comparison of mechanical properties of the 3 PP grades shows that PP-H has a higher yield stress compared to PP-IC and PP-RC and yield stress is significantly higher (yield strain values are lower) than values quoted by the manufacturer. The PhD study has confirmed the process conditions that are able to optimise all the interactive effects to improve functional properties in high volume parts in the packaging industry.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Neste estudo, o comportamento em solução diluída de pré-polímeros uretânicos à base de poli(glicol propilênico) (PPG) e diisocianato de isoforona (IPDI) foi avaliado por medidas viscosimétricas a 30 C em dois tipos de solventes, com diferentes polaridades: isopropanol e tolueno. Os pré-polímeros foram sintetizados em massa, ou seja, na ausência de qualquer solvente, e nas formulações foram variadas as razões entre o número de equivalentes-grama de grupamentos isocianato e hidroxila [NCO/OH] e a massa molar do PPG. Os pré-polímeros foram caracterizados por espectrometria na região do infravermelho. No tratamento matemático dos dados viscosimétricos, foram empregadas cinco diferentes equações para determinar os valores de viscosidade intrínseca: Huggins; Kraemer e Schulz-Blaschke, por extrapolação gráfica; e Solomon-Ciuta; Deb-Chanterjee e; novamente, Schulz-Blaschke, para determinações por um único ponto. Os valores de viscosidade intrínseca obtidos pelos dois métodos (extrapolação gráfica e por um único ponto) foram comparados a fim de se verificar a validade da determinação por um único ponto para os sistemas analisados, bem como determinar qual equação seria a mais adequada para esse tipo de cálculo. Foram calculadas as constantes viscosimétricas de Huggins, Kraemer e Schulz-Blaschke, e foi feita uma análise da qualidade do solvente. / In this study the behavior of urethanes prepolymers based on poly(propylene glycol) (PPG) and isophorone diisocyanate (IPDI), in diluted solutions, were studied by viscosimetric measurements, at 30 C, in two types of solvents with different polarities: isopropyl alcohol and toluene. The prepolymers were synthesized in bulk, i.e, in the absence of solvent. In the formulations were varied the ratio between the equivalent-grams number of isocyanate functional groups and hydroxyl group [NCO/OH] and PPG molecular mass. The prepolymers were characterized by infrared spectrometry (FTIR). Five different equations were used to determine intrinsic viscosities values: Huggins; Kraemer and Schulz-Blaschke, by graphic extrapolation; and Solomon-Ciuta; Deb-Chanterjee and; again, Schulz-Blaschke, by a single point determination. The intrinsic viscosities values obtained by two methods (graphic extrapolations and through a single point determination) were compared in order to verify the validity of the single point determination for the systems studied, as well as the more accurate equation for this type of calculation. Viscometric constants from Huggins; Kraemer and Schulz-Blaschke equations were also determined to verify solvent quality.

Fundação Carlos Chagas Filho de Amparo a Pesquisa do Estado do Rio de Janeiro / Neste estudo, o comportamento em solução diluída de pré-polímeros uretânicos à base de poli(glicol propilênico) (PPG) e diisocianato de isoforona (IPDI) foi avaliado por medidas viscosimétricas a 30 C em dois tipos de solventes, com diferentes polaridades: isopropanol e tolueno. Os pré-polímeros foram sintetizados em massa, ou seja, na ausência de qualquer solvente, e nas formulações foram variadas as razões entre o número de equivalentes-grama de grupamentos isocianato e hidroxila [NCO/OH] e a massa molar do PPG. Os pré-polímeros foram caracterizados por espectrometria na região do infravermelho. No tratamento matemático dos dados viscosimétricos, foram empregadas cinco diferentes equações para determinar os valores de viscosidade intrínseca: Huggins; Kraemer e Schulz-Blaschke, por extrapolação gráfica; e Solomon-Ciuta; Deb-Chanterjee e; novamente, Schulz-Blaschke, para determinações por um único ponto. Os valores de viscosidade intrínseca obtidos pelos dois métodos (extrapolação gráfica e por um único ponto) foram comparados a fim de se verificar a validade da determinação por um único ponto para os sistemas analisados, bem como determinar qual equação seria a mais adequada para esse tipo de cálculo. Foram calculadas as constantes viscosimétricas de Huggins, Kraemer e Schulz-Blaschke, e foi feita uma análise da qualidade do solvente. / In this study the behavior of urethanes prepolymers based on poly(propylene glycol) (PPG) and isophorone diisocyanate (IPDI), in diluted solutions, were studied by viscosimetric measurements, at 30 C, in two types of solvents with different polarities: isopropyl alcohol and toluene. The prepolymers were synthesized in bulk, i.e, in the absence of solvent. In the formulations were varied the ratio between the equivalent-grams number of isocyanate functional groups and hydroxyl group [NCO/OH] and PPG molecular mass. The prepolymers were characterized by infrared spectrometry (FTIR). Five different equations were used to determine intrinsic viscosities values: Huggins; Kraemer and Schulz-Blaschke, by graphic extrapolation; and Solomon-Ciuta; Deb-Chanterjee and; again, Schulz-Blaschke, by a single point determination. The intrinsic viscosities values obtained by two methods (graphic extrapolations and through a single point determination) were compared in order to verify the validity of the single point determination for the systems studied, as well as the more accurate equation for this type of calculation. Viscometric constants from Huggins; Kraemer and Schulz-Blaschke equations were also determined to verify solvent quality.

A viscosimetria é um procedimento experimental simples e pouco oneroso, que pode fornecer informações valiosas sobre o volume hidrodinâmico e a conformação de macromoléculas em solução, num determinado solvente, em uma dada temperatura. Os parâmetros viscosimétricos podem ser matematicamente calculados por extrapolação gráfica, cuja execução experimental é mais demorada. Em contrapartida, é possível que a determinação seja feita por um único ponto. Neste trabalho, os dois métodos de cálculo, empregando uma série de seis equações: Huggins, Kraemer e Schulz-Blaschke, por extrapolação gráfica, e Schulz-Blaschke, Solomon-Ciuta e Deb-Chanterjee por um único ponto, foram utilizados em soluções de poli(glicol propilênico) (PPG) e copolímeros em bloco à base de poli(glicol propilênico) e poli(glicol etilênico) (EG-b-PG), com diferentes teores de poli(glicol etilênico), tendo isopropanol, tetra-hidrofurano (THF) e tolueno como solventes puros, além das misturas em proporções iguais de THF/ isopropanol e THF/ tolueno, a 25C. Os valores de viscosidade intrínseca e de algumas constantes indicaram que os solventes puros e as misturas se apresentaram no limite entre o bom e o mau solvente. Verificou-se também que o método de cálculo por um único ponto foi válido, especialmente quando a equação de Schulz-Blaschke foi empregada, apresentando um baixo percentual de erro sendo possível assim reduzir o tempo de análise para a maioria dos sistemas estudados / The viscosimetry is a simple and inexpensive polymer characterization method that provides valuable information about the hydrodynamic volume and conformation of macromolecules in solution, in a solvent, at a given temperature. The viscosimetric parameters can be mathematically calculated by graphic extrapolation. Nevertheless, these experimental tests demands a lot of time. However, it is possible to achieve results by a single point determination. In this work, the two calculation methods, employing a series of six equations: Huggins, Kraemer and Schulz-Blaschke, by graphic extrapolation; and Schulz-Blaschke, Solomon-Ciuta and Deb-Chanterjee, by a single point determination, were performed in solutions of poly(propylene glycol) (PPG) and block copolymers based on poly(glycol ethylene) and poly(glycol propylene) (EG-b-PG) with different poly (glycol ethylene) segments content. Isopropanol, tetrahydrofuran (THF) and toluene were employed as solvents. Mixtures of equal proportions of THF/ isopropanol and THF/ toluene were utilized as well. The viscosimetric determinations were performed at 25 0,1 C. The values of intrinsic viscosity and of some constants indicated that the pure solvents and the mixtures were in the limit between good and bad solvent. It was also observed that the method of calculation by a single point was valid, specially when Schulz-Blaschke equation was used, showing a low error percentage for most systems studied, reducing the time of analysis