The modeling of Sand Asphalt and experiments to measure their rheological properties are of vital concern to many industrial processes especially highway and roadway pavement construction industry. A variety of hot mix asphalt mixtures are used in highway and runway pavement construction, with each mixture catering to a specific need. These mixtures vary in type and percentage of aggregates and asphalt used and consequently exhibit marked differences in their response. The main thrust of this research is to provide experimental data which would be helpful in determining the efficacy of the constitutive models that have been developed for these hot mix asphalt mixtures. Here we attempt to provide experimental data in the raw form for Sand Asphalt mixtures that would be helpful in the theoretical modeling efforts involving asphalt materials using a continuum point of view. For example the data obtained can be of immense help to evaluate the constitutive model developed by Murali Krishnan and Rajagopal. The Sand Asphalt mixture in their model is modeled as `homogenized' single constituent due to the peculiarity of its makeup. The constitutive model of Murali Krishnan and Rajagopal is based on a thermodynamical framework for materials possessing multiple natural configurations (multiple stress free states) to derive the constitutive equations. Recently an Orthogonal Rheometer was built to characterize the granular solids by Gupta and Rajagopal which was later used by Baek in the torsional mode. In this work we have used the same Torsional Rheometer with some minor modifications in the design to measure some general properties of Sand Asphalt mixtures. Sand Asphalt mixtures, due to their non-linear viscoelastic character, exhibit `normal stress effects' and `stress relaxation'. The Rheometer that we used was able to capture these responses with high precision. We have laid out proper procedures for the further testing of asphalt related mixtures. A typical sand asphalt mixture sample in cylindrical shape was used as the test specimen. From this work some interesting data was obtained. A remarkable observation was that as the shear rate is increased, the normal force and torque generated initially decrease, but beyond a certain shear rate they attain a constant value.

The modeling of Sand Asphalt and experiments to measure their rheological properties are of vital concern to many industrial processes especially highway and roadway pavement construction industry. A variety of hot mix asphalt mixtures are used in highway and runway pavement construction, with each mixture catering to a specific need. These mixtures vary in type and percentage of aggregates and asphalt used and consequently exhibit marked differences in their response. The main thrust of this research is to provide experimental data which would be helpful in determining the efficacy of the constitutive models that have been developed for these hot mix asphalt mixtures. Here we attempt to provide experimental data in the raw form for Sand Asphalt mixtures that would be helpful in the theoretical modeling efforts involving asphalt materials using a continuum point of view. For example the data obtained can be of immense help to evaluate the constitutive model developed by Murali Krishnan and Rajagopal. The Sand Asphalt mixture in their model is modeled as `homogenized' single constituent due to the peculiarity of its makeup. The constitutive model of Murali Krishnan and Rajagopal is based on a thermodynamical framework for materials possessing multiple natural configurations (multiple stress free states) to derive the constitutive equations. Recently an Orthogonal Rheometer was built to characterize the granular solids by Gupta and Rajagopal which was later used by Baek in the torsional mode. In this work we have used the same Torsional Rheometer with some minor modifications in the design to measure some general properties of Sand Asphalt mixtures. Sand Asphalt mixtures, due to their non-linear viscoelastic character, exhibit `normal stress effects' and `stress relaxation'. The Rheometer that we used was able to capture these responses with high precision. We have laid out proper procedures for the further testing of asphalt related mixtures. A typical sand asphalt mixture sample in cylindrical shape was used as the test specimen. From this work some interesting data was obtained. A remarkable observation was that as the shear rate is increased, the normal force and torque generated initially decrease, but beyond a certain shear rate they attain a constant value.

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

This thesis has been done at the powder department (GH) at AB Sandvik Coromant in Gimo. With a rheometer measurements has been made on raw materials and powder blends. The focus of this report has been to find correlations between raw material powders and press data, comparisons have also been made between raw materials and powder blends. The rheometer can show information of how a powder act in flow conditions, together with air and with pressure. Analyses has been done comparing the rheometer data with press parameters (for example: rejected orders, weight variations and the compaction pressure) with the goal to find correlations between the powders flow properties and the powders compaction in production. The measurements and analyses have been showing that the powder flow properties depends on the powders composition and that properties like flow rate, aeration and permeability varies between powder blends and batches of the same powder sort. It seems to exist a correlation between the pressure force and the flow rate of a raw material. This flow rate seems to belong together with the flow rate of the powder blend. No correlations were found between the rheometer measurements and press rejections, weight variations and hall flow values. The statistical analyses that has been used in this report consist of a few number of measured values and for the analyses to be statistic correct it is necessary to have a larger sample in the analyses.

A self-healing material has the inherent ability to partially reverse damage such as crack formation that might have occurred during its service. Significant evidence exists in the literature to indicate that asphalt binder is a self-healing material. It is also well known that healing has a substantial affect on the performance of asphalt mixtures and consequently on the serviceable life of asphalt pavements. For example, shift factors from laboratory experimental data to field observed data show that laboratory data underpredict field observations. There is a need to understand the mechanisms that are responsible for healing in asphalt binders as well as to develop test methods that can be used to determine properties related to these mechanisms. This thesis presents details and findings from a two-part study that addresses each one of these two aspects. In the first part of this study, a test method based on the use of a Dynamic Shear Rheometer (DSR) was developed to determine the parameters of characteristic healing function of asphalt binders. In the second part of this study, Molecular Modeling (MM) techniques were used to determine the interrelationship between molecular structure, surface free energy, self diffusivity, and other healing properties of asphalt binders.The healing characteristic equation parameter (Ro) which represents the instantaneous healing nature of the asphalt binders is analogous to surface energy in terms of effect on healing in asphalt binders. Ro values for three asphalt binders AAM, AAD and ABD are calculated and compared with the surface energy values available from the literature. It was observed that the Ro values are proportional to surface energy values. Surface energy values for five asphalt binders AAM, AAD, AAB, AAG and AAF are calculated using MM method based on SHRP representative molecules. These values were observed to be proportional to the surface energy values from literature. Bulk and surface diffusion coefficients of asphalt molecules are calculated using MM method. Parametric analysis was done to determine the effect of chemical structure of asphalt on its diffusion properties. It was observed that the higher percentage of saturates in the chemical structure results into higher diffusion coefficients.

Polyacrylonitrile (PAN) fiber is one of the most important synthetic fibers in the world because it is a precursor to carbon fiber. Compared to the traditional solution spinning process, the melting spinning process of PAN is less costly and can further reduce the price of PAN fiber. This dissertation is concerned with the objective of establishment of conditions (temperature, plasticizer type, and plasticizer composition) that a PAN copolymer is able to be stable melt spun with water based plasticizers. More specifically, PAN/water/acetonitrile (70/15/15) mixture is considered as reference sample in this study because it was proposed in a BASF patent in which it was claimed it could be stably melt spun. We are looking for a more benign plasticizer so that the use of acetonitrile can be avoided and PAN can still be stably melt spun. To achieve this objective, the first step is to measure the melting point (Tm) of PAN copolymer with various plasticizers and compositions by using differential scanning calorimetry (DSC). The results indicate the Tm of PAN copolymer can be reduced to around 160 oC with water only as a plasticizer, which is lower than the degradation temperature of PAN (180 oC). Moreover, using a water/ethanol mixture and water/acetonitrile as plasticizers can further reduce the melting point of PAN to 150 oC and 135 oC, respectively. The second step is conducting rheological measurements on the PAN/plasticizers mixture. A pressure chamber was designed and attached to the capillary rheometer in order to prevent the foaming and evaporation of plasticizers during the viscosity experiments. Both steady-shear and time-dependent viscosity measurements were conducted. The rheological measurement results indicate that PAN can keep stable for more than 120 minutes with all plasticizers under 170 oC, and it starts to degrade in 60 minutes at 180 oC, except samples plasticized with 30 wt% of water (which keep stable for 120 minutes as well). The steady-shear viscosity results indicate the shear-thinning behavior is observed for the PAN/plasticizer mixtures at a temperature ranging from 170 oC to 190 oC and provide the fundamental viscosity data which can be applied to the extrusion process. In conclusion, the rheological measurements show PAN/Water (70/30 wt%) at 180 oC and PAN/EtOH/Water (70/15/15) at 170 oC are two potential systems for carrying out the PAN melt spinning process. Scanning electron microscopy (SEM) images were taken for the reference state and potential conditions. These images show that the copolymer strands have more and larger voids when plasticized with water only compared to those plasticized with water/acetonitrile and water/ethanol mixture. In this case, PAN/EtOH/Water (70/15/15) at 170 oC is considered to be the most benign system for that PAN melt spinning. / Doctor of Philosophy / The melt spinning process of polyacrylonitrile (PAN) has been studied in the past few decades. Compared to the traditional solution spinning process, it does not require toxic organic solvents. The major problem of the PAN melt spinning process is the melting point (Tm) of PAN is much higher than its degradation temperature. However, by adding plasticizers the Tm of PAN can be significantly reduced, which makes PAN melt spinning feasible. In this work we discuss the feasibility of the melt spinning process of polyacrylonitrile (PAN) copolymer plasticized with water based plasticizers by using differential scanning calorimetry (DSC) and rheological methods. The objective is to use water only as a plasticizer to melt spin PAN under specific conditions (composition, temperature etc). The melting point and rheological measurements have been conducted by DSC and a modified capillary rheometer, respectively, for this plasticized system. The DSC results show that the melting point of the PAN copolymer can be reduced below the degradation temperature of PAN, and the rheological results show that the PAN copolymer can be extruded with a reasonable viscosity at 15-20 o v above its melting point, and also the stability and viscosity are strongly dependent on temperature and the plasticizer type and content. Furthermore, the Scanning electron microscopy (SEM) images show the copolymer strands extruded from PAN/H2O mixture have many more and larger voids than PAN/H2O/EtOH mixture. In conclusion, the results indicate that the most appropriate condition for PAN melt spinning is PAN/H2O/EtOH mixture of 70/15/15 wt% ratio at a temperature of 170 oC

This study aims to better understand the behavior of magnetorheological (MR) fluids operated in the non-conventional squeeze mode through the use of a custom designed rheometer. Squeeze mode is the least understood of the three operational modes of MR fluid and thus its potential has yet to be realized in practical applications. By identifying the behavior of MR fluid in this mode, the foundation for future development of MR technology will be laid. Using the limited amount of literature available on squeeze-mode operation in conjunction with conventional principles associated with MR technology, a custom rheometer was designed and fabricated. A detailed account of the design considerations and background information on the fundamentals incorporated into the design are provided. The squeeze-mode rheometer was used to evaluate a variety of MR fluids to observe trends that may exist across fluids. Specifically, fluids of different ferrous particle volume fractions were considered. Through testing, common trends in fluid stiffness were observed for multiple fluids tested with the squeeze-mode rheometer. When operated in squeeze mode, activated MR fluid has shown to provide substantial resistance to compressive loading, possibly making it attractive for low-displacement high-load systems. The primary observation from the tests is that the activated fluid's stiffness progressively increases over the duration of fluid operation. This phenomenon is due to severe carrier-fluid separation coupled with the formation of ferrous particle aggregate clumps in the fluid. This effect is further explored in this research. / Master of Science

Master of Science / Department of Grain Science and Industry / J.M. Faubion / The market for frozen goods is expanding and the frozen dough goods sector still has potential to expand its market. It is well known that deterioration in bread quality occurs during frozen dough/bread production. In addition, it is known that dough rheology influences bread quality. To prevent deterioration of bread quality, many additives have been used and researched. Combinations of oxidants (potassium bromate and ascorbic acid) are widely used worldwide. However, potassium bromate may be carcinogenic to humans, and it has been detected in bread after baking. Since it has been prohibited or strictly limited in many countries, many researchers have tried to find a replacement. Ascorbic acid is safe for human intake, and does not persist in bread. However, it is not as effective as potassium bromate. Possible replacements in frozen doughs include oxidant (ascorbic acid)-enzyme combinations. This study evaluated the effects of ascorbic acid-specific enzyme combinations as a replacement for the potassium bromate in frozen dough and related the effects to dough behavior (gluten network strength) as evaluated by dynamic oscillation rheometry. Bread quality was evaluated by test baking. Based on the results from fresh baking studies, potassium bromate can be replaced by an optimum level combination of ascorbic acid and hemicellulase/endo-xylanase. This combination clearly improved loaf volume, and crumb grain over both control and potassium bromate containing doughs. For frozen dough/bread production, the addition of all additives improved bread quality, but ascorbic acid and endo-xylanase containing dough resulted in higher volume, and better crumb structure than did dough containing potassium bromate. Dough rheology experiments show that rheology was affected by both the process and additives. Strain sweeps gave the information about dough stability. Both the additives and proofing improved dough stability. Dough behavior (gluten network strength) was assessed by frequency sweeps. Dough containing ascorbic acid and endoxylanase was most stable during frozen dough processing.

Wall slip in the die of a capillary rheometer was investigated. Corn meal and water were mixed to a moisture content of 35% wet basis. Oil was then added at 0%, 2.5%, and 5% of the total mass. A capillary rheometer was used to extrude the mixture at 100C. Three die diameters were studied: 2mm, 4mm, and 8mm. Two length to diameter ratios were studied: L/D=4 and L/D=8. Pressure and flow rate in grams per 30 seconds were collected from the capillary rheometer to perform the Bagley correction, determine the flow behavior index, and correct for slip using the Mooney slip analysis method. Several slip analysis methods were considered prior to the selection of the Mooney method. Overall, the Bagley correction was successful for all die diameters except 2mm. The Mooney method was successful for the 5% added oil content samples. An increase slip velocity was observed as shear stress increased. Mooney plots for 0% and 2.5% resulted in negative shear rate values. An empirical model was developed to predict apparent viscosity of the mixture as a function of total oil content.

Tunneldrivning är tidskrävande med varierande komplexitet från projekt till projekt, där en betydande del av sprängcykeln innefattar att låta injektering härda. Detta är tid där tunneldrivandet står stilla. Ifall denna tid skulle kunna reduceras skulle entreprenörer kunna spara in resurser genom att kunna spränga tidigare. Huvudsyftet med det här examensarbetet är att bidra med förståelse för hur utomstående krafter påverkar injektering. Detta för att man på ett korrekt sätt ska kunna dimensionera och reducera injekteringens härdningstid vid en tunneldrivning. Innan examensarbetets start hade tre olika kravställningar för cementbaserad injektering tagits fram. En del av examensarbetet inkluderade att formulera injekteringsrecept uppfyllande dessa krav, genom att få ökad förståelse för cementbruks reologi.  Genomförandet av arbetet delades upp i tre studier, där cementbruks reologi studerades på olika sätt. Arbetet började med att se hur viskositet och flytgräns ändrades med vattencementtal (VCT) med hjälp av en rheometer (roterande tester). Dessa undersökningar utgjorde studie 1. De vattencementtal som testades var 0,6; 0,8; 1,0 och 1,2. Från denna studie blev värdena höga och ansågs orimliga. Då cement är ett av de reologiskt mest komplicerade materialen rör det sig över stora delar av det viskoelastiska spektret. Det kunde konstateras att vidare studier bör utföras för att öka förståelsen för dels rheometern som mätredskap, dels cementets reologi. I studie 2 mättes samma parametrar som i den första studien, samt inträngningsförmåga, separation och densitet. Dessa tester genomfördes med hjälp av redskapen PenetraCone, Mud Balance, Marshkon, fallkon, muggprover och Yield Stick i laboratoriemiljö. Testerna genomfördes med samma vattencementtal som tidigare, men med två olika sorters cement: Injektering-30 och UltraFine 20. Från dessa tester kunde det konstateras att två av tre krav inte gick att uppfylla med UltraFine 20. Injektering-30 uppfyllde två av kraven med ett vattencementtal på 0,8 och det tredje kravet med ett vattencementtal på 0,6. Dessa resultat försöktes sedan återupprepas i ett fälttest vid Haga station (Västlänken) med blandning i en injekteringsrigg. Två blandningar som skilde sig lite från varandra gjordes under fältstudien. Den ena blandningen gav liknande värden som laboratorietesterna med en något högre flytgräns. Den andra blandningen var något mer lågviskös. Skillnaden mellan dessa två resultat misstänktes bero på skillnaden i tid de fick vara i injekteringsriggen. Det var från början planerat att utföra en ytterligare fältstudie, där Injektering-30 skulle injekteras med vattencementtalet 0,8 i två bergsskärmar. En sprängning skulle därefter ske efter tre timmar, men på grund av förseningar i produktionen har denna fältstudie skjutits upp till våren 2022. Studie 3 bestod av ytterligare rheometer-undersökningar, där oscillerande tester utfördes under en längre tid. Dessa tester gjordes för att se hur cementbrukets viskösa och elastiska skjuvmodul ändrar sig över tid. Genom att göra muggprov parallellt gick det att observera att när cementbruket övergick från att vara dominerat visköst till att vara dominerande elastiskt så ändrades brottsmekanismen i bruket. Cementbruket gick från att flyta fritt till att det uppstod ett cirkulärt skjuvbrott (okulärt observerat). Med resultatet från de oscillerande testerna delades cementets härdningsprocess in i fyra olika steg. Det första steget är när cementpartiklarna flyter vid ett muggprov (egentyngden är större än materialets flytgräns). Det andra steget är när bruket övergår från dominerande visköst till dominerande elastiskt och brottet som nu uppstår är ett cirkulärt skjuvbrott. Det tredje steget är när cementet härdat tillräckligt så att cirkulära skjuvbrott inte uppstår i ett muggprov. I detta stadie går det att peta ett hål i cementet utan att det läker sig själv. Det fjärde och sista steget är när cementen härdat så pass mycket att materialet börjat bete sig mycket sprödare och är som starkast.  För att kunna sätta en preliminär plan för dimensionering av härdningstid på cementbruket, så beräknades kraften som cementbruket upplever som en funktion av töjningarna i berget vid detonation. Detta gjordes med hjälp av Hookes lag och de oscillerande testerna som utfördes under längre tid för att mäta skjuvmodulen. Med detta så togs följande preliminära plan fram, för beräkning av härdningstiden på cementbaserad injektering:  Mät maximala deformationen i berget Mät den komplexa skjuvmodulen på bruket över tid   Ta reda på förväntad maximal sprickvidd Beräkna skjuvtöjning   Beräkna last     Gör fallkontest för att ta reda på hållfastheten i bruket Jämför teoretisk last och hållfasthet för bruket och se när hållfastheten blir större än teoretisk last Spräng efter den beräknade tiden. Planen har inte testats i praktiken och vidare studier behöver utföras. Sammanfattningsvis lägger examensarbetet grunden för vidare studier inom detta ämne. Indikationer från arbetet visar att härdningstiden teoretiskt bör gå att förkorta. Det spekuleras ifall det skulle gå att förkorta härdningstiden ytterligare ifall något sorts mikrofibrer eller likande används som armering i cementen, för att motverka det cirkulära skjuvbrottet som verkar uppstå. Det är självklart av yttersta vikt att denna armering inte påverkar inträngningsförmågan i någon större utsträckning / Tunnel excavation is time demanding with varying complexity. A significant part of the tunnel excavation cycle consists of letting grout harden. This is time where the excavation basically is put on hold. If this part of the excavation cycle could be reduced, the contractor would be able to save resources by conducting blasting earlier. The main purpose with this master thesis is to contribute with knowledge regarding how external forces affects grout. This is of significance to be able to design and to reduce the grout’s hardening time correctly. Before this master’s thesis began three different requirements for cement grout had been developed. One part of this master’s thesis included formulating grout recipes to fulfill these requirements, by gaining further knowledge regarding cement grout rheology. The execution of this work was divided into three part-studies where cement rheology was studied in different ways. The work started by investigating the water cement ratios influence on cements viscosity and yield point by performing rotating tests with a rheometer. This investigation was a part of study 1. The water cement ratios which were studied was 0.6, 0.8, 1.0 and 1.2. It was concluded that the results were way to high and was deemed unreasonable. Cement is rheologically one of the most complex materials, because it spans over great parts of the viscoelastic spectrum. It was concluded that further studies should be performed to further understand both how the rheometer works and cements rheology.  In study 2, the same parameters were measured as in the previous study with the addition of penetrability, separation, and density. These tests were performed with PenetraCone, Mud Balance, Marsh funnel, fall cone, mug tests and Yield Stick tests in a laboratory environment. The tests were conducted with the same water cement ratios as in study 1, but with two different brands of cement: Injektering-30 and UltraFine 20. From these tests the conclusion was that it was not possibly to fulfill two out of the three requirements with UltraFine20 whereas Injektering could fulfill all three requirements. Two out of the three requirements were fulfilled with a water cement ratio of 0.8. These results were then further investigated in a field environment at station Haga in Gothenburg. Two batches were produced, where one of the batches became slightly less viscous than the other and the lab results. It is believed that this was because the less viscous batch spent a longer amount of time in the mixer.  From the start, another field study planned to be conducted where Injektering-30 would be used as grout with a water cement ratio of 0.8. A blast would then be detonated after three hours. Due to delays in the excavation of Haga Station this study was postponed to spring 2022. Study 3 consisted of further rheometer-investigations where oscillating tests were performed during a longer period of time, to see how the shear modulus changed over time. These tests measured the viscous and elastic shear modulus of the cement. By doing parallel mug tests it was observed that when the cement went from dominant viscous to dominant elastic the failure mechanism of the cement changed. The cement went from flowing freely to what looks like a circular shear failure (ocularly observed). With the results from the oscillating test, the cement’s hardening process was divided into four different stages. In the first stage, the particles flow freely (weight of particles are greater than the materials yield point). In the second stage the cement will be more elastic than viscous, and a circular shear failure occurs. In the third stage, the grout has hardened enough so a circular shear failure won’t occur in a mug test. It is now possible to point a hole in the cement without it flowing, and it will heal itself. In the fourth and final stage the cement has hardened enough that the cement has a high strength and behaves brittle.  To estimate a preliminary plan to design the hardening time on cement the forces on the grout has been calculated as a function of the deformations in the surrounding rock. This was done using Hookes law and the oscillating tests which was performed during a longer period of time to measure the shear modulus. With this logic the following plan was introduced, to design the grouts hardening time: Measure deformations in the rock Measure the complex shear modulus of the grout over time  Find the maximum joint width  Calculate shear strain Calculate load Do fall cone tests to determine the strength of the grout Compare theoretical load with strength of the grout and see when the strength becomes greater than the load  Perform blasting after calculated time.  This plan has not yet been tested and need further studies to determine its validity.  In conclusion this master’s thesis is the groundwork to further studies regarding this subject. Indications from this work shows that the hardening time could theoreticality be reduced. One could speculate if it would be possible to shorten the hardening time even further by introducing some kind of reinforcement to the grout, which would prevent the observed circular shear failure. It is obviously important that the reinforcement does not interfere with the penetrability of the grout.