The influence of particle shape of coating pigments on theirpacking ability and on the flow properties of coating colourshas been investigated. The particle shapes considered werespherical, flaky and acicular (needle-shaped). In the case ofsuspensions containing monodisperse spherical polystyreneparticles, a concentration gradient appeared in the filter cakeforming during filtration under static conditions. Such agradient, monitoredby non-destructive magnetic resonanceimaging (MRI), is not accounted for in the traditionalfiltration theory used in coating technology. Good agreementwas found between a literature model describing filtrationthrough a compressible filter cake and the concentrationgradients measured by MRI. According to this model, the scaledconcentration gradient was the same at all times. For flaky (mainly kaolin) and acicular (aragonite)particles, a rapid method was evaluated to estimate a shapefactor of the pigment particle. Generalised mathematical modelsof oblate and prolate spheroids were applied to reduce thethree geometrical dimensions of the particle to two, the majoraxis and the minor axis. The shape factor, which is mass-based,was derived from a comparison between the results obtained bytwo different size-assessment instruments, viz. the Sedigraphand an instrument using light scattering. This yields a shapefactor distribution as a function of equivalent sphericalparticle size, but the results are uncertain for small particlediameters, below 0.2 µm. Good agreement was obtainedbetween the shape factor and a mass-based aspect ratio obtainedby image analysis, but the rapid method is generally moreaccurate for flaky than for acicular particles. Results obtained by capillary viscometry showed that therewas a relationship between the viscosity at high shear rates(&gt;105s-1) and the shape factor, but that it was notsufficient to use the median value of the shape factor toachieve proper information. A more complete evaluation requiresknowledge of the shape factor distribution, which is also givenin part by the method mentioned above. However, a large medianshape factor was related to a high high-shear viscosity.Non-Newtonian entrance pressure losses were sometimessignificant in capillary viscometry, indicating that it wasinappropriate to measure the shear viscosity with only onecapillary. Such effects were however relatively much morepronounced in slit die viscometry, especially in the case ofacicular particles, where the aspect ratio was a crucialparameter. The influence of the shape factor of kaolinparticles on the non-Newtonian entrance pressure losses over aslit die was surprisingly small. The high-shear viscosity ofcoating suspensions based on different pigments correlated withthe median pore size of the corresponding coating layer ratherthan with the porosity. <b>Keywords</b>: Aspect ratio, capillary viscometry, coatingcolour, filtration, particle packing, pigment, pore structure,rheology, shape factor, slit die viscometry, spheroid.

<p>The influence of particle shape of coating pigments on theirpacking ability and on the flow properties of coating colourshas been investigated. The particle shapes considered werespherical, flaky and acicular (needle-shaped). In the case ofsuspensions containing monodisperse spherical polystyreneparticles, a concentration gradient appeared in the filter cakeforming during filtration under static conditions. Such agradient, monitoredby non-destructive magnetic resonanceimaging (MRI), is not accounted for in the traditionalfiltration theory used in coating technology. Good agreementwas found between a literature model describing filtrationthrough a compressible filter cake and the concentrationgradients measured by MRI. According to this model, the scaledconcentration gradient was the same at all times.</p><p>For flaky (mainly kaolin) and acicular (aragonite)particles, a rapid method was evaluated to estimate a shapefactor of the pigment particle. Generalised mathematical modelsof oblate and prolate spheroids were applied to reduce thethree geometrical dimensions of the particle to two, the majoraxis and the minor axis. The shape factor, which is mass-based,was derived from a comparison between the results obtained bytwo different size-assessment instruments, viz. the Sedigraphand an instrument using light scattering. This yields a shapefactor distribution as a function of equivalent sphericalparticle size, but the results are uncertain for small particlediameters, below 0.2 µm. Good agreement was obtainedbetween the shape factor and a mass-based aspect ratio obtainedby image analysis, but the rapid method is generally moreaccurate for flaky than for acicular particles.</p><p>Results obtained by capillary viscometry showed that therewas a relationship between the viscosity at high shear rates(>10⁵s^-1) and the shape factor, but that it was notsufficient to use the median value of the shape factor toachieve proper information. A more complete evaluation requiresknowledge of the shape factor distribution, which is also givenin part by the method mentioned above. However, a large medianshape factor was related to a high high-shear viscosity.Non-Newtonian entrance pressure losses were sometimessignificant in capillary viscometry, indicating that it wasinappropriate to measure the shear viscosity with only onecapillary. Such effects were however relatively much morepronounced in slit die viscometry, especially in the case ofacicular particles, where the aspect ratio was a crucialparameter. The influence of the shape factor of kaolinparticles on the non-Newtonian entrance pressure losses over aslit die was surprisingly small. The high-shear viscosity ofcoating suspensions based on different pigments correlated withthe median pore size of the corresponding coating layer ratherthan with the porosity.</p><p><b>Keywords</b>: Aspect ratio, capillary viscometry, coatingcolour, filtration, particle packing, pigment, pore structure,rheology, shape factor, slit die viscometry, spheroid.</p>

The degree of polymerization (DP) is the main factor which plays a role in cellulose aging. The adverse consequence of cellulose fibers aging is the deterioration of mechanical and optical properties. Viscometry is a technique which is frequently used for determination of degree of polymerization of cellulose fibers. The aim of the work was to determine the degree of polymerization of cotton fabrics and to investigate the dependence of DP on number of washing and dying. Next task was to investigate if there exists a corellation between DP and results from thermal and thermo-oxidative degradation studied by methods of thermal analysis. First, the traditional viscometry was employed to determine DP of cellulose fibers. It has been demonstrated that number of washing and dying decreases the DP. In the second part the differential scanning calorimetry (DSC) and thermogravimetry (TG) were used. DSC provided values of combustion heat and TG allowed the detail evaluation of degradation steps; obtained results were further used for correlation with DP. Methods of thermal analysis revealed differences between cotton wool and treated fabrics. Combustion heat did not show any correlation with DP. In contrast, results from TG suggested some promising correlations which could be used for the prediction of cotton fabrics DP using thermal analysis in the future.

No description available.

Hyaluronic acid is commonly used in dermatological fillers in the form of gels. It is established how these gels' firmness is affected by the amount of cross linker and hyaluronic acid respectively. However, the effect of hydroxide ions in solution is rather unknown. This thesis examines how the alkalinity of the solvent affects the intrinsic viscosity of 3 MDa hyaluronic acid by using the method of Ubbelohde capillary viscometry. Sodium hydroxide solutions between 2 and 10 wt% were prepared to study the variation in intrinsic viscosity at concentrations relevant for cross linking (1&lt;wt%). From these respective solutions, four solutions of different mass concentrations of hyaluronic acid were made. The flow time of respective samples were measured between two points in the capillary viscometer in a controlled temperature of 25 °C with an SI Viscoclock to ensure a high accuracy.From the resulting flow times, the intrinsic viscosity was calculated. The intrinsic viscosity varied between 0,55 and 0,70. The relation between intrinsic viscosity and hydroxide ion concentration had a correlation coefficient r &lt; 0,001. No trend could be ensured as the confidence interval for the intrinsic viscosity at the different concentrations was too large.

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&#61616; 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&#61616; 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&#61616; 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&#61616; 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.

Dans le but d’approfondir les connaissances fondamentales entre la structure des polymères associatifs intramoléculaires (polysavons) et leurs propriétés physico-chimiques en milieux aqueux, trois nouvelles familles de polymères amphiphiles cationiques ont été synthétisées par deux méthodes complémentaires permettant une grande variabilité de structure. Les polymères obtenus sont des poly(méth)acrylamides en peigne avec des groupes latéraux de type ammonium quaternaire portant une chaîne alkyle de taille variable. Une étude du comportement physico-chimique de ces polymères en solution, par viscosimétrie et spectroscopie de fluorescence avec deux sondes aux caractéristiques complémentaires, montre qu’ils présentent des propriétés de polysavons qui varient progressivement avec la structure des polymères amphiphiles étudiés, notamment la longueur de la chaîne alkyle latérale, la taille de l’espaceur entre les deux sites polaires amide et ammonium quaternaire et la masse molaire moyenne en nombre. En parallèle, la tensiométrie a montré que ces polyamphiphiles ont une très faible activité à l’interface eau/air confirmant la prédominance de l’effet hydrophobe, alors que les modèles moléculaires correspondants présentent d’excellentes propriétés tensio-actives. Des films de Langmuir ont ensuite été réalisés dans le cadre de la première étude de cette importance sur des polyamphiphiles cationiques. Dans ce domaine également, la grande variabilité de structure des polymères a permis des observations originales et de dégager de nouvelles relations entre la structure du polymère et les caractéristiques des isothermes de compression obtenues / In order to improve the fundamental knowledge of the relationships between the chemical structure of intramolecular associative polymers (polysoaps) and their physical chemical properties in aqueous media, three new families of cationic amphiphilic polymers were obtained by complementary methods offering great structure variability. The corresponding polymers were comb poly(meth)acrylamides with pendant ammonium groups with alkyl side chains of variable lengths. A first investigation of their physical chemical behaviour in aqueous solutions, by viscometry and fluorescence spectrometry with two complementary fluorescent probes, showed that they displayed polysoap properties which varied progressively with their chemical features, in particular the length of the alkyl side chain, the size of the spacer between the two polar amide and ammonium groups and the polymer molecular weight. Tensiometry confirmed the prevailing of the hydrophobic effect by showing that these polymers displayed a very weak activity at the water/air interface although the corresponding molecular models showed excellent tensio-active properties. Langmuir’s films were eventually obtained in the first study of this importance on cationic amphiphilic polymers. Here again, the great structural variability enabled original observations and new structure/properties relationships were obtained for the corresponding compression isotherms

<p>Cellulose ethers and polyethylene glycols are used in drug formulations as water swelling or water soluble matrices. Polar lipids, for example monoglycerides, and surfactants can be used to solubilise hydrophobic or amphiphilic drugs and to formulate potential drug delivery vehicles such as emulsions, liposomes and cubic phases. In this thesis mixtures of these excipients are characterised in various environments, from dilute aqueous solutions to solid dispersions. Special focus has been on the understanding of the associating processes involved.</p><p>Detailed understanding of the association of cellulose ethers, of varying hydrophobicity, and amphiphilic substances is presented. The hydrophobicity of the polymer was found to have an impact on the interaction scheme. The amphiphiles were found to bind at lower amphiphile concentrations to a more hydrophobic polymer thus influencing both micro- and macroscopic structure of the aggregates. </p><p>The choice of counterion to the amphiphile has a small but significant effect on the interaction and the structure of the aggregates. Also amphiphilic drug molecules can interact with nonionic polymers in a similar way as surfactants in aqueous solution. Due to the higher cmc of the drug ibuprofen the interaction is largely influenced by the ionic strength of the solution. The type of amphiphile also influences the cooperativity of the amphiphile-polymer binding.</p><p>In more concentrated systems liquid crystals are formed into which the polymer interact with the amphiphiles. Both cubic and sponge phases were found with relatively large polymers interacting with polar lipids. These phases were found to swell and shrink mainly controlled by the amount of polymer inside them. Also membrane interacting substances added to the sponge phase could influence the size of the water channels in the phase. </p><p>In water free systems polymers and polar lipids were found to interact as well as forming solid dispersions. The behaviour of the phase separation between polymer and lipid depended on the concentration of the dispersed phase. The polar lipid was found to be distributed in the lamellar part of the semicrystalline polymer influencing the polymer folding.</p>

Cellulose ethers and polyethylene glycols are used in drug formulations as water swelling or water soluble matrices. Polar lipids, for example monoglycerides, and surfactants can be used to solubilise hydrophobic or amphiphilic drugs and to formulate potential drug delivery vehicles such as emulsions, liposomes and cubic phases. In this thesis mixtures of these excipients are characterised in various environments, from dilute aqueous solutions to solid dispersions. Special focus has been on the understanding of the associating processes involved. Detailed understanding of the association of cellulose ethers, of varying hydrophobicity, and amphiphilic substances is presented. The hydrophobicity of the polymer was found to have an impact on the interaction scheme. The amphiphiles were found to bind at lower amphiphile concentrations to a more hydrophobic polymer thus influencing both micro- and macroscopic structure of the aggregates. The choice of counterion to the amphiphile has a small but significant effect on the interaction and the structure of the aggregates. Also amphiphilic drug molecules can interact with nonionic polymers in a similar way as surfactants in aqueous solution. Due to the higher cmc of the drug ibuprofen the interaction is largely influenced by the ionic strength of the solution. The type of amphiphile also influences the cooperativity of the amphiphile-polymer binding. In more concentrated systems liquid crystals are formed into which the polymer interact with the amphiphiles. Both cubic and sponge phases were found with relatively large polymers interacting with polar lipids. These phases were found to swell and shrink mainly controlled by the amount of polymer inside them. Also membrane interacting substances added to the sponge phase could influence the size of the water channels in the phase. In water free systems polymers and polar lipids were found to interact as well as forming solid dispersions. The behaviour of the phase separation between polymer and lipid depended on the concentration of the dispersed phase. The polar lipid was found to be distributed in the lamellar part of the semicrystalline polymer influencing the polymer folding.