Thesis (Ph.D.) - University of Queensland, 2005. / Includes bibliographical references.

Thesis (Ph. D.)--University of Idaho, October 2006. / Major professor: Chien M. Wai. Abstract. Includes bibliographical references. Also available online in PDF format.

Thesis (Ph. D.)--University of Idaho, May 2006. / Major professor: Chien M. Wai. Includes bibliographical references. Also available online in PDF format.

No description available.

Interest in high-pressure and supercritical fluids as physical blowing agents for polymer foaming is driving a renewed need for the fundamental understanding of polymer thermophysical and rheological properties in the presence of dense fluids. In particular, carbon dioxide is often studied as a physical blowing agent because of its readily accessible critical point (31.1 ℃ and 73.8 MPa) and relatively high solubility levels in polymer materials. The basic principle involved is to dissolve the supercritical fluid in the polymer at high pressures and then impose a pressure reduction to initiate bubble nucleation and growth. The outcomes depend on the thermophysical and rheological properties of the polymer under the prevailing process conditions in the fluid. The present dissertation explores the high-pressure characterization and foaming of thermoplastic elastomers and seeks to link polymer thermophysical and rheological properties to polymer foaming outcomes with carbon dioxide as a physical blowing agent. A major focus of this dissertation has been the development of novel high-pressure characterization techniques to understand polymer behavior at high pressure. These techniques include (1) high-pressure torsional braid analysis (HP-TBA), (2) magnetic suspension balance (MSB), and (3) unique high-pressure batch foaming cells. HP-TBA allows for the assessment of the depression in thermal transitions (Tg and/or Tm/Tc) and the changes in rheological properties like modulus or rigidity of polymer systems exposed to carbon dioxide. MSB provides for the assessment of the amount of carbon dioxide that sorbs into a polymer material at a given temperature and pressure. Unique confined foaming strategies have been developed to translate information learned from batch-scale experimentation to practical industrial applications. The polymer systems of interest are thermoplastic elastomers including poly(ethylene-co-vinyl acetate) (EVA) and poly(ethylene-co-vinyl acetate-co-carbon monoxide) (EVACO). These materials find use in numerous commercial applications including adhesives, compatibilizers, and foams. Their foams are noted to undergo significant degrees of expansion followed by unfavorable post-foaming collapse. In the first part of this study, the foaming of neat EVACO and EVA with carbon dioxide was explored. The blending of these polymers was then explored to regulate foam expansions and control the pore morphology development. The foamability of the polymers and their blends was explored under both isothermal and gradient conditions to assess the temperature effects on foaming outcomes at a given pressure. In the second part of this study foaming of EVACO was explored in relationship to the depressed thermal transitions of the polymer in the presence of carbon dioxide. Accompanying the depressed melting transition is a sharp reduction in the modulus or rigidity of the polymer material. By studying foaming outcomes near the melting transition rational windows for foaming exploration can be evaluated to generate foams that display more favorable bulk foam densities and minimal foam collapse. This part demonstrates that linking foaming conditions to the relative rigidity or melt strength of EVACO in carbon dioxide allows for the determination of the lower pressure where foaming will occur and the upper pressure beyond which further foam density reductions are not significant. The third part of this study explores the foaming of EVACO with carbon dioxide under batch, confined foaming conditions where the foam expansion is restricted in order to again control the foaming outcomes and prevent foam collapse. A practical question is the scale-up of batch foaming processes which likely will be conducted with injection molding or extrusion type processes. Studying batch foaming in confinement allows for a better understanding of the factors that may affect foam development that may be more readily translated to industrial practice. The fourth part of this study examines the role of crystallinity and block copolymer composition in altering the polymer behavior in carbon dioxide. Several EVACO polymers with varying ethylene, vinyl acetate, and carbon monoxide content have been explored to study how block copolymer composition affects the thermophysical and rheological properties along with the sorption of carbon dioxide at high pressure. / Doctor of Philosophy / Polymers, colloquially referred to as plastics, are used as the materials to generate foams like the sole of a tennis shoe or the Styrofoam coffee cup on your desk. Currently, these materials are made using environmentally damaging and potentially health hazardous chemicals that are gradually being phased out by global regulations. Producing polymer foams, or foaming, using compressed carbon dioxide is a more environmentally favorable process to generate porous or "foamed" materials. It is crucial to understand how the polymer behaves in a high-pressure environment with gases such as carbon dioxide to manufacture these materials. Several unique instruments were developed to understand polymer behavior in carbon dioxide, allowing for insights into polymer material behavior at high pressure. This information can then be translated into selecting temperature, pressure, and saturation conditions from which to generate polymer foams. The polymers of interest are rubbers that display elastic behavior like a classic rubber band. They are of interest in athletic equipment, tennis shoes, or other areas where repetitive compression and recovery properties are essential. In the first part of this study blending of two polymer systems was explored to see how blending alters foaming outcomes. In the second part, foaming was explored in relationship to the material behavior of the polymer in the presence of carbon dioxide. Specifically, this part involves the study of foaming near the melting transition, which is the transition where the polymer material loses its ordered structure. Studying foaming outcomes near the melting transition allows rational windows for foaming exploration to be evaluated to generate foams that display more favorable bulk foam densities and minimal foam collapse. The third part explores the foaming of polymers with carbon dioxide under batch confined foaming conditions where the foam expansion is restricted to control the foaming outcomes again and prevent foam collapse. A practical question is the scale-up of batch foaming processes which likely will be conducted with injection molding or extrusion type processes. Studying batch foaming in confinement allows for a better understanding of the factors that may affect foam development that may be more readily translated to industrial practice. The fourth part examines a series of polymers that display different degrees of elasticity. This study allows for understanding how elasticity may impact foaming outcomes like the collapse observed after the foam is generated.

The motivation for the determination of the viscosity of polymer solutions in dense fluids at the critical polymer concentration stems from the need to understand the factors that influence the time scale of phase separation in systems that undergo spinodal decomposition upon a pressure quench. In a recent investigation of PDMS + CO₂ and PE + n-pentane where molecular weights of the polymers and the critical polymer concentrations were comparable, significant differences were observed in the time evolution of new phase growth. Among the reasons that contribute to the difference in phase separation kinetics is the viscosity of the solutions. This thesis has been carried out to experimentally demonstrate the differences in viscosities of solutions at their critical polymer concentration. Specifically, the thesis focused on the high-pressure density and viscosity of solutions of poly(dimethylsiloxane) (Mw = 93,700, Mw/Mn = 2.99) in supercritical carbon dioxide and of polyethylene (Mw = 121,000, Mw/Mn = 4.3) in near-critical n-pentane. The measurements have been carried out at the critical polymer concentrations, which is 5.5 wt % for solution of PDMS in CO2 and 5.75 wt % for solution of PE in n-pentane. For PDMS + CO₂ system, the measurements were conducted at 55, 70, 85 and 100 oC and pressures up to 50 MPa. For PE + n-pentane system, the measurements were conducted at 140 and 150 °C and again up to 50 MPa. All measurements were conducted in the one-phase homogenous regions. At these temperatures and pressures, the viscosities were observed to be in the range from 0.14 mPa.s to 0.22 mPa.s for PDMS + CO₂, and from 2.3 mPa.s to 4.6 mPa.s for PE + n-pentane systems. In both systems the viscosities increase with pressure and decrease with temperature. The temperature and pressure dependence could be described by Arrhenius type relationships in terms of flow activation energy (E#) and flow activation volume (V#) parameters. The flow activation energies in PDMS + CO₂ system were about 7 kJ/mol compared to about 18 kJ/mol for the PE + n-pentane system. The activation volumes were in the range 40-64 cm3/mol for PDMS + CO₂ system and 65-75 cm3/mol for the PE + n-pentane solution. The higher values of E# and V# represent the higher sensitivity of viscosity to temperature and pressure changes in the PE + n-pentane system. The viscosity data could also be correlated in terms of density using free-volume based Doolittle type equations. Density is shown to be an effective scaling parameter to describe T/P dependency of viscosity. The closed packed volumes suggested from density correlations were found to be around 0.33 cm³/g for the PDMS and 0.48 cm3/g for the PE systems. Comparison of the viscosity data in these systems with the data on the kinetics of pressure-induced phase separation confirms that the slower kinetics in the PE + n-pentane stems from the higher viscosity in this solution compared to the PDMS + CO₂ system, despite the similarity in the molecular weight of the polymer and the critical polymer concentrations. These viscosity and density measurements were conducted in a special falling-body type viscometer. In the course of this thesis a more reliable procedure for determining the terminal velocity of the falling sinker was implemented. This is based on the precise and more complete description of the position of the sinker with time with the aid of a set of linear variable differential transformers (LVDTs). The design of the new arrangement and procedure for terminal velocity determination and calibration procedures for the viscometer are also presented. The densities and viscosities are determined with an accuracy of ± 1 % and ± 5 % or better, respectively. / Master of Science

Lubrication theory plays a fundamental role in all mechanical design as well as applications to biomechanics. All machinery are composed of moving parts which must be protected against wear and damage. Without effective lubrication, maintenance cycles will be shortened to impractical levels resulting in increased costs and decreased reliability. The focus of the work presented here is on the lubrication of rotating machinery found in advanced power systems and designs involving micro-turbines. One of the earliest studies of lubrication is due to Osborne Reynolds in 1886 who recorded what is now regarded as the canonical equation governing all lubrication problems; this equation and its extensions have become known as the Reynolds equation. In the past century, Reynolds equation has been extended to include three-dimensional effects, unsteadiness, turbulence, variable material properties, non-newtonian fluids, multi-phase flows, wall slip, and thermal effects. The bulk of these studies have focused on highly viscous liquids, e.g., oils. In recent years there has been increasing interest in power systems using new working fluids, micro-turbines and non-fossil fuel heat sources. In many cases, the design of these systems employs the use of gases rather than liquids. The advantage of gases over liquids include the reduction of weight, the reduction of adverse effects due to fouling, and compatibility with power system working fluids. Most treatments of gas lubrication are based on the ideal, i.e., low pressure, gas theory and straightforward retro-fitting of the theory of liquid lubrication. However, the 21st Century has seen interest in gas lubrication at high pressures. At pressures and temperatures corresponding to the dense and supercritical gas regime, there is a strong dependence on gas properties and even singular behavior of fundamental transport properties. Simple extrapolations of the intuition and analyses of the ideal gas or liquid phase theory are no longer possible. The goal of this dissertation is to establish the correct form of the Reynolds equation valid for both low and high pressure gases and to explore the dynamics predicted by this new form of the Reynolds equation. The dissertation addresses five problems involving our new Reynolds equation. In the first, we establish the form appropriate for the simple benchmark problem of two-dimensional journal bearings. It is found that the material response is completely determined by a single thermodynamic parameter referred to as the "effective bulk modulus". The validity of our new Reynolds equation has been established using solutions to the full Navier-Stokes-Fourier equations. We have also provided analytical estimates for the range of validity of this Reynolds equation and provided a systematic derivation of the energy equation valid whenever the Reynolds equation holds. The next three problems considered here derive local and global results of interest in high speed lubrication studies. The results are based on a perturbation analysis of our Reynolds and energy equation resulting in simplified formulas and the explicit dependence of pressure, temperature, friction losses, load capacity, and heat transfer on the thermodynamic state and material properties. Our last problem examines high pressure gas lubrication in thrust bearings. We again derive the appropriate form of the Reynolds and energy equations for these intrinsically three-dimensional flows. A finite difference scheme is employed to solve the resultant (elliptic) Reynolds equation for both moderate and high-speed flows. This Reynolds equation is then solved using perturbation methods for high-speed flows. It is found that the flow structure is comprised of five boundary layer regions in addition to the main ``core'' region. The flow in two of these boundary layer regions is governed by a nonlinear heat equation and the flow in three of these boundary layers is governed by nonlinear relaxation equations. Finite difference schemes are employed to obtain detailed solutions in the boundary layers. A composite solution is developed which provides a single solution describing the flow in all six regions to the same accuracy as the individual solutions in their respective regions of validity. Overall, the key contributions are the establishment of the appropriate forms of the Reynolds equation for dense and supercritical flows, analytical solutions for quantities of practical interest, demonstrations of the roles played by various thermodynamic functions, the first detailed discussions of the physics of lubrication in dense and supercritical flows, and the discovery of boundary layer structures in flows associated with thrust bearings. / Doctor of Philosophy / Lubrication theory plays a fundamental role in all mechanical design as well as applications to biomechanics. All machinery are composed of moving parts which must be protected against wear and damage. Without eective lubrication, maintenance cycles will be shortened to impractical levels resulting in increased costs and decreased reliability. The focus of the work presented here is on the lubrication of rotating machinery found in advanced power systems and designs involving micro-turbines. One of the earliest studies of lubrication is due to Osborne Reynolds in 1886 who recorded what is now regarded as the canonical equation governing all lubrication problems; this equation and its extensions have become known as the Reynolds equation. In the past century, Reynolds equation has been extended to include three-dimensional eects, unsteadiness, turbulence, variable material properties, non-newtonian uids, multi-phase ows, wall slip, and thermal eects. The bulk of these studies have focused on highly viscous liquids, e.g., oils. In recent years there has been increasing interest in power systems using new working uids, micro-turbines and non-fossil fuel heat sources. In many cases, the design of these systems employs the use of gases rather than liquids. The advantage of gases over liquids include the reduction of weight, the reduction of adverse eects due to fouling, and compatibility with power system working uids. Most treatments of gas lubrication are based on the ideal, i.e., low pressure, gas theory and straightforward retro-tting of the theory of liquid lubrication. However, the 21st Century has seen interest in gas lubrication at high pressures. At pressures and temperatures corresponding to the dense and supercritical gas regime, there is a strong dependence on gas properties and even singular behavior of fundamental transport properties. Simple extrapolations of the intuition and analyses of the ideal gas or liquid phase theory are no longer possible. The goal of this dissertation is to establish the correct form of the Reynolds equation valid for both low and high pressure gases and to explore the dynamics predicted by this new form of the Reynolds equation. The dissertation addresses ve problems involving our new Reynolds equation. In the rst, we establish the form appropriate for the simple benchmark problem of two-dimensional journal bearings. It is found that the material response is completely determined by a single thermodynamic parameter referred to as the eective bulk modulus. The validity of our new Reynolds equation has been established using solutions to the full Navier-Stokes-Fourier equations. We have also provided analytical estimates for the range of validity of this Reynolds equation and provided a systematic derivation of the energy equation valid whenever the Reynolds equation holds. The next three problems considered here derive local and global results of interest in high speed lubrication studies. The results are based on a perturbation analysis of our Reynolds and energy equation resulting in simplied formulas and the explicit dependence of pressure, temperature, friction losses, load capacity, and heat transfer on the thermodynamic state and material properties. Our last problem examines high pressure gas lubrication in thrust bearings. We again derive the appropriate form of the Reynolds and energy equations for these intrinsically threedimensional ows. A nite dierence scheme is employed to solve the resultant (elliptic) Reynolds equation for both moderate and high-speed ows. This Reynolds equation is then solved using perturbation methods for high-speed ows. It is found that the ow structure is comprised of ve boundary layer regions in addition to the main core region. The ow in two of these boundary layer regions is governed by a nonlinear heat equation and the ow in three of these boundary layers is governed by nonlinear relaxation equations. Finite dierence schemes are employed to obtain detailed solutions in the boundary layers. A composite solution is developed which provides a single solution describing the ow in all six regions to the same accuracy as the individual solutions in their respective regions of validity. Overall, the key contributions are the establishment of the appropriate forms of the Reynolds equation for dense and supercritical ows, analytical solutions for quantities of practical interest, demonstrations of the roles played by various thermodynamic functions, the rst detailed discussions of the physics of lubrication in dense and supercritical ows, and the discovery of boundary layer structures in ows associated with thrust bearings.

The use of compressed CO2 processing to alter the pore size, structure and timescale of silica condensation in surfactant templated silica thin films and powders is investigated by systematically varying the template structure and CO2 processing conditions. Tailoring the mesoporous materials increases its potential applications, as demonstrated in catalysis, drug delivery, chromatographic and electrode applications. This work demonstrates for the first time the applicability of fluorinated surfactants as templates for the synthesis of mesoporous silica thin films by dip coating. Well-ordered films with 2D hexagonal close-packed pore structure are synthesized in an acid-catalyzed medium using three cationic fluorinated templates of varied tail length and branching (C6F13C2H4NC5H5Cl, C8F17C2H4NC5H5Cl and (CF3)2CFC5F9C2H4NC5H5Cl). CO2 processing of the fluorinated templated silica results in a significant and controlled increase in pore diameter relative to the unprocessed films. The pore expansion is significantly greater compared to the negligible expansion observed in hydrocarbon (C16H23NC5H5Br) templated silica. The greater swelling of the fluorinated templates is attributed to the favorable penetration of CO2 in the CO2-philic fluorinated tail and the relative solvation of each template is interpreted from their interfacial behavior at the CO2-water interface. The CO2 based pore expansion observed in fluorinated surfactant templated films is extended successfully to base-catalyzed silica powders templated with a fluorinated surfactant (C6F13C2H4NC5H5Cl). Pore expansion in silica powders is significantly less than in acid catalyzed films and demonstrates the effects of pH on surfactant selfassembly in CO2 and increased silica condensation at basic conditions, which inhibits pore expansion. Finally, the use of fluorescence probe molecules is demonstrated for in-situ monitoring of the of CO2 processing of surfactant templated silica films to provide time dependent data on the local environment and dynamics of CO2 penetration. CO2 uptake occurs in surfactant tails even for hydrocarbon templates (C16H23N(CH3)3Br and C16H23NC5H5Br), which display negligible CO2 based swelling of the resulting pores. The timescale of silica condensation increases significantly in the presence of CO2 suggesting opportunities for structure alteration through application of external forces, such as magnetic fields and change in substrate chemistry and system humidity

A Copaifera langsdorffii é uma das plantas de incentivo governamental para pesquisas científicas e possui diversas atividades biológicas. Em especial, as atividades antitumoral e tripanocida foram abordadas neste estudo tendo o ácido caurenoico (AC) como marcador. Devido à escassa literatura sobre a extração do AC e à sua baixa solubilidade, sua extração foi estudada com solvente orgânico e por fluido supercrítico. A extração por fluido supercrítico é vantajosa já que não fornece extratos com resíduos de solventes orgânicos e é ecologicamente correta. Visto as atividades antitumoral e tripanocida do AC e estas atividades serem objeto de estudo nacional e mundial, o AC foi inserido em lipossomas convencionais e furtivos com a finalidade de torná-lo mais biodisponível, permitir seu alcance ao sítio-alvo e diminuir seus efeitos adversos. Assim, os objetivos deste trabalho foram segmentados em três vertentes: a) realizar o estudo e otimização da extração do ácido caurenoico a partir das folhas de C. langsdorffii, b) obter lipossomas convencionais, secá-los pelos métodos de secagem liofilização (FD), spray drying (SD) e spray freeze drying (SFD), comparar suas características físico-químicas e avaliar suas atividade antitumoral e tripanocida, c) obter lipossomas furtivos e avaliar sua seletividade tumoral. De maneira geral, os resultados das extrações sólido-líquido e por fluido supercrítico apresentaram boa seletividade e eficiência visto que foram capazes de fornecer extratos com aproximadamente 20% de AC. A extração por fluido supercrítico foi mais eficaz extraindo 26,2% de AC. Já os lipossomas convencionais secos por SD e SFD apresentaram-se mais semelhantes entre si quanto à propriedade de fluxo e morfologia, à interação do AC com os componentes da bicamada lipídica e à dissolução/ liberação que quando secos por FD. Os três métodos de secagem foram capazes de prolongar em seis meses a estabilidade do AC nos lipossomas quando comparado com a dispersão aquosa. Os lipossomas convencionais secos apresentaram citotoxicidade maior frente a células tumorais e menor frente a células normais quando carregados com o AC e comparados com os lipossomas convencionais vazios (sem AC). Foi possível sintetizar com sucesso o lipídeo ligado ao polietilenoglicol e ao ácido fólico com o intuito de preparar os lipossomas furtivos. Entretanto, estes lipossomas não apresentaram ação antitumoral seletiva quando comparados às células normais. / Copaifera langsdorffii is one of the Brazilian plants which receives governmental support for scientific researches and also presents several biological activities. The kaurenoic acid (KA) is a diterpenic acid constituent of this specie that presents, in special, antitumoral and tripanocide activities which were taken into account in this study. Due to the lack of KA extraction from C. langsdorffii leaves in the literature and to KA low solubility, its extraction was studied using solid-liquid and supercritical fluid extraction methods. The supercritical fluid extraction is advantageous since provides solvent-free extracts and is an environment friendly method. Since KA is antitumoral and tripanocide and both activities are subject of national and internacional studies, in this study, KA was added in conventional and stealth liposomes in order to increase its biodiponibility, to allow it reaching the target tissue and decrease its adverse effects. So, this work was divided in three segments: a) study and optimize the KA extraction from C. langsdorffii leaves by solid-liquid (SLE) and supercritical fluid (SFE) extraction methods, b) obtain conventional liposomes, dry them by freeze drying (FD), spray drying (SD) and spray freeze drying (SFD), compare their physico-chemical features and evaluate their antitumor and tripanocide activities, c) obtain stealth liposomes and evaluate their selective tumor activity. In a general way, the extraction methods result in high KA selective extraction by both SLE and SFE since they were able to extract nearly 20% of KA. The SFE was a bit more efficacious than SLE providing 26,2% of KA. Conventional liposomes dried by SD and SFD were more similar in fluidity and morphology, KA and liposome lipid compounds interaction and dissolution/ release than liposomes dried by FD. The three drying methods provided more stable liposomes than the aqueous solution liposomes. Dried conventional liposomes presented higher cytotoxicity to tumor cells and lower one to normal cells when loaded with KA than unloaded conventional liposomes. The lipid linked to poliethyleneglycol and to folic acid to prepare stealth liposomes were successfully synthesized. However, the stealth liposomes did not presented selective antitumor action in relation to normal cells.

Neste trabalho estudamos as propriedades estruturais e eletrônicas do CO2 supercrítico, iniciando com a avaliação de campos de força balizados por aplicações anteriores de simulação quântica do tipo Dinâmica Molecular de Born-Oppenheimer (BOMD). A aplicação principal é a descrição do espectro de absorção da paranitroanilina (pNA) em CO2 supercrítico. O CO2 supercrítico pode ser considerado como uma ``alternativa verde para os solventes orgânicos convencionais e a busca por solventes mais seguros, juntamente com a crescente consciência sobre a questão ambiental, tem levado a uma ``química verde com o intuito de se buscar soluções sustentáveis. A princípio estudamos três campos de força tradicionais para o CO2, aplicados na região supercrítica. Estes campos de força podem ser validados por meio de simulação de primeiros principios. Iniciamos considerando a condição supercrítica para o CO2 como T = 315 K, = 0.81 g/cm³ e o campo de força clássico de Zhang e Duan. Depois fizemos uma análise consistindo de uma alteração de cargas e também da geometria do CO2, que seria um caso não linear no qual foi considerado um ângulo (O-C-O) = 176° . O estudo do solvatocromismo da pNA em CO2 supercrítico foi feito considerando todas estas situações descritas para o campo de força, avaliando os resultados experimentais e teóricos já existentes. A simulação gera estruturas usando Monte Carlo e são usadas em cálculos de Mecânica Quântica do tipo DFT (CAM-B3LYP). Por fim, para verificar a importância da geometria do sistema, ou seja, a propriedade estrutural, consideramos uma outra geometria para a pNA, diferente da geometria que utilizamos a princípio nas simulações com o CO2 supercrítico. Essa ``geometria modificada\" da pNA foi obtida de uma simulação existente de Born-Oppenheimer e a utilizamos numa simulação Monte Carlo com o caso não linear para o CO2 supercrítico. Os resultados de todas essas simulações nos indicaram que a alteração das cargas e por consequência a alteração da polarização do solvente, não possui muita importância na mudança do espectro de absorção da pNA. Ao se considerar o CO2 não linear, obtivemos resultados um pouco melhor, mas não muito, comparados com a previsão teórica. Mas os resultados mais significativos são os obtidos para a situação em que utilizamos a geometria modificada da pNA. Uma parte do deslocamento do máximo da banda de absorção no espectro da pNA vem com a contribuição eletrostática da interação soluto-solvente e a outra parte vem da mudança estrutural. / In this work we study the structural and electronic properties of CO2 supercritical starting with the evaluation of force fields based on previous ab initio Born-Oppenheimer molecular dynamics (BOMD). The main application is the description of the absorption spectrum of paranitroanilina (pNA) in supercritical CO2. The supercritical CO2 is considered a ``green alternative\" to conventional organic solvents and the search for safer solvents, along with the increasing awareness of environmental issues has led to the interest in ``green chemistry\", seeking sustainable solutions. At first we studied three traditional force fields for CO2, applied in the supercritical region. These force fields can be validated by first principles simulation. We considered the supercritical condition for CO2 as T=315K, =0.81g/cm³ and the classical force field of Zhang and Duan. We also did an analysis consisting of a change of the atomic point charges and the geometry of CO2, including a non-linear case in which an angle (O-C-O)=176° was considered. The study of the solvatochromism of pNA in supercritical CO2 was made considering all these situations, evaluating the theoretical outcome and the experimental results. The simulation generates structures using Monte Carlo and are used in quantum mechanics calculations of DFT (CAM-B3LYP). To verify the importance of geometry in the system, that is, the structural property, we considered another geometry for the pNA geometry different from that we used initially in the simulations with supercritical CO2. This ``modified geometry\" of pNA was obtained from a previous Born-Oppenheimer simulation and was used in a Monte Carlo simulation with the non-linear case for supercritical CO2. The results of all these simulations indicated that the alterations of charge and thus the change in the polarization of the solvent, has no great importance in the change of the absorption spectrum of the pNA. When considering the nonlinear CO2, we obtained slightly better results. But the most significant results are obtained for the situation in which we use the modified geometry of pNA. Part of the shift in the absorption spectrum of the pNA comes with the electrostatic contribution of solute-solvent interaction and the other part comes from the structural change.