This thesis discusses and documents the validation efforts related to Ontario’s LS-299 and LS-308 test methods which are two new test methods developed for the performance-based specification grading of asphalt cement. In addition, this report presents the field validation of a simple performance indicator, loss tangent, for specification grading of asphalt cement for thermal cracking. Furthermore, another objective of this study is to investigate and compare the low temperature fracture and rheological behavior of engineered asphalt materials from field and laboratory-aged test sections on Highway 655 in northern Ontario. Extracted asphalt cements from 20 contract sites in eastern and northeastern Ontario were tested according to Ontario’s LS-299 and LS-308 test methods. It was found that all good performing contracts that showed little or no distress showed low grade losses in LS-308 and retained high strain tolerances as measured in LS-299 compared to the poor performing contracts. Asphalt cements recovered from these 20 contract sites in eastern and northeastern Ontario were also tested in torsion bar geometry to determine their viscoelastic properties. It was decided to focus on the phase angle, as a more direct measure for low temperature performance. Phase angle is a very sensitive parameter to small changes in rheology as the phase angle is approximately equal to the derivative of the logarithm of the stiffness with respect to frequency. It was found that tan() was able to distinguish good from poor performers with 95% accuracy after only a short period of conditioning prior to testing. This is a considerable improvement over the current low temperature bending beam rheometer protocol. Black space diagrams, frequency sweeps, Cole-Cole plots, and master curves were generated for comparison of field and laboratory aged materials from the Highway 655 trial in northern Ontario. The findings show that chemical hardening occurs much faster in the field than through laboratory ageing methods. Also, reversible ageing of binders may occur at low temperatures and could be linked to field performance. Furthermore, a high low temperature phase angle appears to be a reasonable indicator for thermal cracking resistance. / Thesis (Master, Chemistry) -- Queen's University, 2009-08-28 15:12:29.845

Yes / The viscoelastic nature of polymeric formulations utilised in drug products imparts unique thermomechanical attributes during manufacturing and over the shelf life of the product. Nevertheless, it adds to the challenge of understanding the precise mechanistic behaviour of the product at the microscopic and macroscopic level during each step of the process. Current thermomechanical and rheological characterisation techniques are limited to assessing polymer performance to a single phase and are especially hindered when the polymers are undergoing thermomechanical transitions. Since pharmaceutical processing can occur at these transition conditions, this study successfully proposes a thermomechanical characterisation approach combining both mechanical and rheological data to construct a comprehensive profiling of polymeric materials spanning both glassy and rubbery phases. This approach has been used in this study to assess the mechanical and rheological behaviour of heterogenous polymer blends of hydroxypropyl cellulose (HPC) and hydroxypropyl methylcellulose (HPMC) over a shearing rate range of 0.1–100 s−1 and a temperature range of 30–200 °C. The results indicate that HPC and HPMC do not appear to interact when mixing and that their mixture exhibits the mechanistic properties of the two individual polymers in accordance with their ratio in the mixture. The ability to characterise the behaviour of the polymers and their mixtures before, throughout, and after the glassy to rubbery phase transition by application of the combined techniques provides a unique insight towards a quality-by-design approach to this and other polymer-based solid dosage forms, designed with the potential to accelerate their formulation process through obviating the need for multiple formulation trials.

The main objective in this work was to learn how the instrument, the Interfacial Shear Rheometer (ISR400), worked and to investigate how the rheological properties, storage modulus (elasticity), G' and loss modulus (viscous), G'', changes when the surface pressure at the air-liquid interphase changes. The second objective were to examine the different kind of magnetic needles used in the experiments and to conclude which type of needle is best for its specific field of analysis. It was concluded that the relative heavy needle with mass 70.6 mg and length 50 mm was best for systems where the viscous and elastic components are significantly large, where the inertia of the needle is not dominant. It also worked of using the heavier needle for a system of phospholipids. For the hydroxystearic acid (HSA) experiment that were tested on NaCl sub-phase there was a clear improvement after switching from the heavy needle (mass 41.5 mg; length 51 mm) to the relative lighter needle (mass 6.94 mg; length 34.7 mm). The values for the dynamic modulus therefore had a better agreement with reference literature. A spread layer of class II hydrophobins (HFBII) could be compressed to a surface pressure of 46 mNm-1. The G' and G'' values from the frequency sweep were discarded because the monolayer turned into a very viscous-like liquid, and the oscillating needle, after compression, was kind of stuck in the sub-phase and moved very staggering during a frequency sweep. The needle comparison experiment with silica particles 10 wt% Bindzil CC30 (BCC30), at pH 3.5 was done to see if there was any difference in the sensitivity for the needles at the interface which consisted of a pure 10 mM NaCl solution or a 10 mM NaCl solution with BCC30 added to it. The differences were negligible in terms of surface tension but there was a clear difference between the heavy needle and the light needle, when oscillating at higher frequencies (>≈6 rad/s). With this study, the understanding of ISR400 has increased largely. Several issues have been addressed and the results provide a good basis for further studies within the many areas the instrument can be used for. Despite the project's time limit, and the fact that the instrument was new and untested where the project was carried out, focus areas were prioritized so good results could be achieved within reasonable goals. / Huvudmålet med detta arbete var att lära sig hur instrumentet ytskiktsreometern (ISR400) fungerade och undersöka hur de reologiska egenskaperna, elasticitetsmodulen G' och viskositetsmodulen G'', kommer att förändras när det sker en förändring för yttrycket vid gränsskiktet mellan luft och vätska. Det sekundära målet var att undersöka vilken typ av magnetiska nålar som är bäst att använda för respektive gränsskiktssystem. Av att använda den tyngre nålen med massan 70.6 mg och längden 50 mm kunde man dra slutsatsen att den är bäst att använda för system där de viskösa och elastiska komponenterna är signifikant stora, där nålens tröghet inte är dominant. Den fungerade även att mäta med i ett fosfolipidsystem. I experimentet med 12-hydroxy-stearinsyra (HSA) som utfördes på en subfas av NaCl, syntes en klar förbättring efter att byta från en tyngre nål (massa 41.5 mg; längd 51 mm) till en lättare (massa 6.94 mg; längd 34.7 mm). Värdena för dynamiska modulen stämde därför bättre överens med referenslitteraturen. Det utspridda lagret av klass II hydrophobins (HFBII) kunde komprimeras upp till yttrycket 46 mNm-1. Värdena för G' och G'' förkastades därför att monolagret förvandlades till en väldigt viskösliknande vätska, och den oscillerande nålen, efter kompressionen, satt fast i denna tröga vätska och rörde sig väldigt hackigt och oregelbundet under tiden ett frekvenssvep utfördes. Då en jämförelse av olika typer av nålar genomfördes med kiseldioxidpartiklar (10 % (viktsprocent) Bindzil CC30 med pH 3.5), för att se om det är någon skillnad i känslighet för nålarna vid gränssnittet, som bestod av en ren 10 mM NaCl-lösning eller en 10 mM NaCl-lösning med tillsatt BCC30. Skillnaderna var försumbara gällande ytspänningen, men det var en klar skillnad mellan den tunga nålen och den lätta nålen vid oscillering vid höga frekvenser (>≈6 rad/s). I och med detta arbete så har förståelsen för hur ISR400 fungerar förbättrats mycket sedan starten. Flera frågeställningar har behandlats och resultaten ger en bra grund för fortsatta studier inom de många områden som utrustningen kan användas till. Trots projektets tidsbegränsning, och det faktum att instrumentet var nytt och oprövat på platsen där detta arbete utfördes, så prioriterades fokusområden så att goda resultat kunde uppnås inom rimliga mål.

Asphalt mixtures are complex composites that comprise aggregate, asphalt binder, and air. Several research studies have shown that the mechanical behavior of the asphalt mixture is strongly influenced by the matrix, i.e. the asphalt binder. Therefore, accurate constitutive models for the asphalt binders are critical to ensure accurate performance predictions at a material and structural level. However, researchers who use computational methods to model the micromechanics of asphalt mixtures typically assume that (i) asphalt binders behave linearly in shear, and (ii) either bulk modulus or Poisson’s ratio of asphalt binders is not time dependent. This research develops an approach to measure and model the shear and bulk behavior of asphalt binders at intermediate temperatures. First, this research presents the findings from a systematic investigation into the nature of the linear and nonlinear response of asphalt binders subjected to shear using a Dynamic Shear Rheometer (DSR). The DSR test results showed that under certain conditions a compressive normal force was generated in an axially constrained specimen subjected to cyclic torque histories. This normal force could not be solely attributed to the Poynting effect and was also related to the tendency of the asphalt binder to dilate when subjected to shear loads. The generated normal force changed the state of stress and interacted with the shear behavior of asphalt binder. This effect was considered to be an “interaction nonlinearity” or “three dimensional effect”. A constitutive model was identified to accommodate this effect. The model was successfully validated for several different loading histories. Finally, this study investigated the time-dependence of the bulk modulus of asphalt binders. To this end, poker-chip geometries with high aspect ratios were used. The boundary value problem for the poker-chip geometry under step displacement loading was solved to determine the bulk modulus and Poisson’s ratio of asphalt binders as a function of time. The findings from this research not only improve the understanding of asphaltic materials behavior, but also provide tools required to accurately predict pavement performance. / text

The main objectives of this research were twofold: 1). to develop advanced material characterization techniques for bitumen, mastic and mortar aiming to improve the knowledge of the behavior of asphalt concrete at micro and meso scales, and 2). to develop an efficient macro-mechanical numerical model capable of determining flexible pavement responses to traffic and environmental loads.

[pt] As propriedades reológicas na interface ar/água de modelos de surfactantes pulmonares (DPPC, DPPC:DPPG, DPPC:DPPG:Colesterol, Survanta e Curosurf) foram investigadas utilizando técnicas de cisalhamento superficiais (reometria de cisalhamento interfacial) e dilatacionais (tensiometria da gota pendente). Assim, alguns parâmetros de interesse foram obtidos para o estudo da viscoelasticidade das amostras (como viscosidade e módulos de armazenamento e perda) e as limitações das técnicas também foram analisadas. Os experimentos foram realizados de forma dinâmica, em que a faixa de frequência de interesse abrange, inclusive, a frequência respiratória de um atleta. Os resultados obtidos mostram a maior viscosidade do Survanta, frente ao Curosurf, e mostram o caráter intermediário do DPPC, que pode ser alterado pela adição de DPPG (aumentando a elasticidade) e Colesterol (aumentando a viscosidade), sugerindo que a mistura DPPC:DPPG pode ser mais adequada do que com DPPC:DPPG:COL para simular o comportamento do surfactante pulmonar. A reometria dilatacional não se mostrou aplicável ao estudo dos surfactantes, o que pode ser causado pela alta viscoelasticidade e relativa instabilidade do Survanta. / [en] The interfacial rheological properties of lung surfactants models (DPPC, DPPC:DPPG, DPPC:DPPG:Cholesterol, Survanta and Curosurf) at the air/water interface were investigated using shear (interfacial shear rheometry) and dilatacional (pendent drop tensiometry) techniques. Thus, some parameters of interest were obtained to study the viscoelasticity of the samples (such as viscosity and storage and loss modules) and the limitations of the techniques were also analyzed. The experiments were carried out dynamically, in which the interest frequency range includes the respiratory rate of an athlete. The results obtained show the higher viscosity of Survanta, compared to Curosurf, and show the intermediate character of DPPC, which can be altered by addition of DPPG (increasing the elasticity) and Cholesterol (increasing the viscosity), suggesting the DPPC:DPPG mixture may be more suitable than with DPPC:DPPG:CHOL to simulate the lung surfactant behavior. The dilatacional rheometry does not shown to be applicable for surfactants studies, which can be caused by the high viscoelasticity and relative instability of Survanta.

The Diploma thesis is focus on polymer modified bitumen for warm mix asphalt. The theoretical part of the thesis describes additives which influence the properties of bitumen for their use and reduction of production and service temperatures. Further, the theoretical part describes the conclusions from the researches. This part also describes empirical and functional tests of bituminous binders. The practical part presents the results of individual tests. Tests were performed on samples of non-aged, aged by RTFOT and RTFOT + PAV methods. The results of the work and the assessment of the suitability of bituminous binders are summarized at the end of the thesis.

The diploma thesis is focused on polymer modified binders with different polymer doses. The theoretical part describes the history of the use of bitumen, the extraction of bitumen from oil and behavious of the polymer type SBS/SB, which is used in the diploma thesis on modified binders. Further, the theoretical part describes the empirical and functional tests of bitumen binders. In the practical part the results of indidual tests are presented and compared with the standard ČSN 65 7222-1. At the end of the diploma thesis are summarized results of work and evaluation of binders with the best achieved properties.

The thesis describes the relaxation properties of bituminous binders determined in dynamic shear rheometer (DSR). Paving bitumen, polymer modified bitumen (PMB) and crumb rubber modified bitumen (CRmB) were chosen for comparison. In order to describe the effects of ageing on asphalt binders relaxation properties, the laboratory simulation of ageing using RTFOT and 3xRTFOT method was performed. For each binder were simultaneously conducted tests of needle penetration, softening point and elastic recovery. Selected bitumens were used for the production of asphalt mixtures. The low-temperature properties tests (TSRST) were performed for these mixtures, when the results were compared to the relaxation properties of binders determined in the DSR.

The theoretical part of this thesis describes the rheology of bituminous binders, aging of asphalt binders and laboratory methods simulating short and long term aging. The following describes an empirical tests (needle penetration, softening point ring ball method) and functional tests (complex shear modulus and phase angle, dynamic viscosity), which are performed in the dynamic shear rheometer. At the end of this section, laboratory aging of bituminous binders using method RTFOT and method RTFOT + PAV is described in more detail. In the practical part of this thesis, the results of all tests performed on the binders aged using RTFOT + PAV are introduced and compared with results of properties of non-aged binders and binders aged by 3xRTFOT.