This doctoral thesis consists of a literature review, presented in two papers, and another six papers describing experimental studies of the influence of different kinds of wax and polyphosporic acid on bitumen and asphalt concrete mixture properties. The literature review should give an extensive description of the field of knowledge concerning wax in bitumen. Effects of wax in crude oil, bitumen and asphalt concrete as well as test methods for studying these effects are described. Theories behind possible mechanisms are also discussed, and commercial wax as additive to bitumen for different purposes included. The experimental parts comprise laboratory studies involving totally five 160/220 penetration base bitumens from different sources, two isolated bitumen waxes, five commercial waxes and one polyphosphoric acid. Asphalt concrete slabs, containing base or modified bitumen were prepared and tested. Binder properties were evaluated using different types of laboratory equipment, such as dynamic shear rheometer (DSR), bending beam rheometer (BBR), differential scanning calorimeter (DSC), force ductilometer, as well as equipment for determining conventional parameters like penetration, softening point, viscosity, and Fraass breaking point. Fourier Transform Infrared (FTIR) spectroscopy and Thin Layer Chromatography (TLC-FID) were used for chemical characterization. The binders were aged by means of the rolling thin film oven test (RTFOT) and pressure ageing vessel (PAV) in combination. Asphalt concrete properties were evaluated at low temperatures using the tensile strain restrained specimen test (TSRST) and creep test at -25°C. Dynamic creep testing was performed at 40°C, as well as complex modulus tests between 0 and 20°C. Binder test results indicated that the magnitude and type of effect on bitumen rheology depend on the bitumen itself, type of crystallizing fraction in the bitumen and/or type and amount of additive used. Bitumen composition was found to be of decisive importance. Adding polyethylene wax or polyphosphoric acid, especially to a non-waxy 160/220 penetration grade bitumen, showed no or positive effects on the rheological behaviour at low temperatures (decrease in stiffness) as well as medium and high temperatures (increase in complex modulus and decrease in phase angle). However, the corresponding positive effects could not be shown in dynamic creep testing (at 40°C) of asphalt concrete mixtures containing these modified binders. Adding FT-paraffin decreased the physical hardening index for all bitumens. Also polyethylene wax and montan wax showed this effect for some bitumens. Slack wax showed a large increasing effect on physical hardening, and polyphosphoric acid none or a minor negative effect. No correlation between physical hardening index (PHI) and wax content by DSC was found in this study, involving both natural bitumen wax and commercial wax. Addition of the commercial waxes used showed no or marginally positive influence on bitumen ageing properties for the bitumens and test conditions used. Comparing asphalt mixture test results to the corresponding binder test results, the effects on asphalt mixtures from adding commercial wax or polyphosphoric acid were less evident. Significant binder physical hardening by BBR could not be confirmed by TSRST. / QC 20101006

The diploma thesis is focused on the design and production of two innovative asphalt mixtures of the VMT 22 type into the base asphalt course. The newly produced blends contain modified binders, such as polymer modified bitumen (PMB) and Crumb rubber modified bitumen (CRMB). The theoretical part of the thesis describes the current state of the use of Reclaimed asphalt pavement in the base asphalt course. Furthermore, there are described types of asphalt mixtures for the base asphalt course are used in the Czech Republic and other countries. The conclusion of the theoretical part is devoted to the description of Reclaimed asphalt pavement (RAP), its storage and processing in a hot mix center. In the practical part of this thesis, there is described design and test of two High modulus asphalt mixture VMT 22, into which 25% RAP is dosed cold without rejuvenators. These asphalt mixtures are then subjected to functional tests (Stiffness of asphalt mixture test, Resistance to fatigue test, Low temperature properties of asphalt mixture test). The results of the functional tests are compared with the functional requirements in the Czech regulation TP 151. In the end of this thesis it is verified by means of the LayEps software that a suitable design of the asphalt mixture can significantly extend the road life.

Subject of this diploma thesis is to describe the effect of adding different amount of aged binder recovered from RAP on the change of properties of polymer modified bitumen. The RAP containing unmodified bitumen and the RAP where we can expect bitumen modification are used to recover binder. The binder obtained from RAP is dosed into the virgin binder in amount of 15 %, 30 % and 50 %. The methods of recycling of flexible pavements, extraction and regeneration of asphalt binders, rejuvenating of their properties and methods of empirical and functional laboratory tests are described in the theoretical part. The practical part deals with evaluating and comparison of the results mixed binders properties.

Thesis (MScEng)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: Chip and spray surfacing seals has been widely used in South Africa as the preferred surface treatment for rural roads. The design of these seals has also experienced renewed interest and continuous development in several other countries over the past two decades. In South Africa seals are continually used as increasing attention is given to the periodic maintenance of existing surfaced roads. There is also a significant increase in the use of surfacing seals in North America as the need to develop more energy and resource efficient surfacing options becomes a priority. Despite this growing use of surface seals, the seal design and especially the selection of binder type and grade does not always follow scientific processes. Seals are often designed based on client preference, previous experience, material availability and industry trends. With an ageing road network and limited funding to ensure timeous maintenance, the focus in South Africa is moving towards more stringent and scientific design processes. The USA and Europe, forced by increasing traffic volumes and heightened performance demands, are moving towards performance- based specification to account for deficiencies in their current surface seal design methods. One of the major failure mechanisms of surface seals is ravelling which takes place when the binder and the aggregate bond becomes weak and are broken by the forces generated by traffic. This leads to loose aggregate on the road which in turns leads to bare surface patches and broken windscreens. To prevent and address this as part of the development of performance-based specifications, the need for a simple and inexpensive technique for evaluating bitumen and bitumen emulsion bond strength development over time, as well as binder-aggregate compatibility, was identified. Although various tests exist for investigating adhesion between bituminous emulsions and aggregate chips most of the tests does not deliver the level of information required by the performance-based specifications. The Bitumen Bond Strength (BBS) test method was therefore developed with the aim to address some of the limitations encountered in evaluating bond strength between binders and aggregates. The BBS test (AASHTO TP-91, 2011) was developed by the University of Wisconsin – Madison (UWM) in partnership with the University of Ancona – Italy (UAI) and the University of Stellenbosch – South Africa (US) specifically for evaluating bond strength between aggregates and hot applied binders and emulsions, respectively. US became involved in BBS test efforts in 2008 to assist in the development and practical evaluation of the BBS test method. UAI contributed significantly to the development of the test apparatus through their work in conjunction with UWM. Due to time and resources available, the involvement of the US was limited to various discussion sessions, a study tour, the evaluation of the BBS test, and conducting a series of control tests. By using the Bitumen Bond Strength test it was possible to evaluate the practicality and repeatability of the developed procedure and the results measured was successfully used to evaluate the bond strength development of modified and unmodified bitumen emulsions on tillite and granite aggregates. It was also possible to correlate the results achieved at the University of Stellenbosch with results from the University of Wisconsin-Madison due to the fact that testing took place at both institutions. The development of the test and the inter-laboratory test results in essence reinforced the hypothesis that the BBS test protocol can be used to effectively evaluate bond strength of different emulsion types and aggregate types. Except for the loading rate which is a known critical influence, the emulsion type and curing intervals are both identified as the most significant other factors contributing to bond strength development. Aggregate type is also identified as a significant factor that will influence the bond strength development. Interactions between emulsion type and curing interval are identified as the most significant interaction. A lot of further validation test on the BBS test method is still required for the test to be integrated into a performance-based specification system for surface seals. / AFRIKAANSE OPSOMMING: “Chip and Spray” oppervlak seëls is die verkose seël tipe vir gebruik op Suid Afrikaanse plattelandse paaie. Die ontwerp van hierdie tipe seëls is ook tans besig om hernude aandag te trek in heelwat lande. In Suid Afrika word die tipe seël al meer gebruik soos die behoefte na herseël projeke op die verouderde pad netwerk groei . Daar is ook heelwat groei in die gebruik van “Chip en Spray” seëls in Noord Amerika aangesien daar n behoefte is om n meer energie en materiaal effektiewe seëls te gebruik. Ten spyte van die groeiende gebruik van hierdie seëls het daar min wetenskaplike ontwikkeling plaasgevind in the ontwerp daarvan. Seëls word meestal ontwerp gebaseer op klient voorkeur , ondervinding, materiaal beskikbaarheid en ook industrie norms. ‘n Verouderde pad netwerk dwing die Suid Afrikaanse industrie om meer deeglike en wetenskaplike ontwerp prosedures te volg. Die VSA en Europa word deur vinnig groeiende verkeersvolumes en verhoogte kwaliteits behoeftes gedwing om prestasie gebaseerde spesifikasies te ontwikkel. Een van die hoof defekte op seëls is klipverlies wat plaasvind as die verbinding tussen die bitumen en aggregaat verswak en gebreek word deur die kragte wat deur verkeer oorgedra word. Dit lei tot los klip op die pad wat weer tot skade aan voertuie lei. Om dit te voorkom en aan te spreek het die behoefte laat ontwikkel vir n maklike en goedkoop tegniek om te meet hoe sterk die verbinding is wat ontwikkel tussen verskillende bitumen, bitumen emulsies en aggregaat monsters. Alhoewel daar alreeds toetse bestaan wat kan toets hoe sterk die verbinding is , gee die meeste van die toetse nie die informasie wat benodig word deur die voorgestelde prestasie gedrewe spesfikasies nie. Die “Bitumen Bond Strength” (BBS) toets metode is daarom ontwikkel om die tekortkoming in die toets van die bitumen en aggregaat verdindinge aan te spreek. Die BBS toets (AASHTO TP-91, 2011) is ontwikkel by die Universiteit van Wisconsin – Madison (UWM) in vennootskap met die Universiteit van Ancona – Italy (UAI) en die Universiteit van Stellenbosch (US) , spesifiek om die die sterkte van die verbinding wat vorm tussen aggregaat en bitumen te meet. Die US het in 2008 betrokke geraak by die BBS toets studie om hulp te verleen met die ontwikkeling en praktiese evalueering van die BBS toets metode. As gevolg van tyd en personeel tekorte is die betrokkendheid by die US beperk tot verskeie besprekings sessies, n studie toer, die evalueering van die BBS toets sowel as die voltooing van n uitgebreide stel toetse. Deur die voltooing van eksperimente met die BBS toets was dit moontlik om die uitvoerbaarheid en herhaalbaarheid van die ontwikkelde prosedure te toets. Die resultate van die toetse is suksesvol gebruik om die ontwikkeling van die verbinding sterkte tussen gemodifiseerde en ongemodifiseerde bitumen emulsies en tilliet en graniet te definïeer en te evalueer. Dit was ook moontlik om die resultate van die Universiteit Stellenbosch en die Universiteit of Wisconsin-Madison suksesvol met mekaar te vergelyk aangesien toetse by beide die instansies voltooi is. Die ontwikkeling van die toets en die inter laboratorium toets resultate het dit moontlik gemaak om die hipotese te bevestig dat die BBS toets prosedure effektief gebruik kan word om die bitumen en aggregaat verdindinge te toets en te evalueer. Behalwe vir die tempo van die lading waarteen die aftrek sterkte getoets word , is die emulsie tipe en die nabehandeling tydperk beide geidentifiseer as die mees beduidende invloede wat bydrae tot die ontwikkeling van die verbinding sterkte. Die aggregaat tipe is ook geidentifiseer as n belangrike faktor wat die verbinding sterkte ontwikkeling sal beïnvloed. Die interaksie tussen die emulsie tipe en nabehandeling tydperk was geïdentifiseer as die mees beduidende interaksie. Daar sal wel nog heelwat eksperimente voltooi moet word met die BBS toets prosedure voordat dit volkome geïntegreer kan word as deel van n prestasie gebaseerde spesifikasie stelsel vir die ontwerp van seëls.

Thesis (MScEng)--Stellenbosch University, 2014. / ENGLISH ABSTRACT: This research investigates the flexibility and the performance properties of bitumen stabilised materials under the influence of mix variables. The laboratory testing consisted of two main phases. During the first phase (mix design), the strength and the flexibility of the mixes were assessed through ITS (Indirect Tensile Strength), UCS (Unconfined Compressive Strength), displacement at break, strain at break and fracture energy. The second phase consisted of a series of triaxial tests done to assess the performance properties (shear strength: cohesion and angle of internal friction; and stiffness: resilient modulus) of the mixes. The mineral aggregates used in this study were milled from different locations of the R35, near Bethal. This was a blend of granular material (dolerite, from various locations of the existing base and subbase layer of the R35) and Reclaimed Asphalt (RA) milled from the existing surfacing. During the mix design phase, two types of bituminous binders were used (bitumen emulsion and foamed bitumen) at bitumen content ranges of 2%, 2.4% and 2.8% each. Two types of active filler were used separately and in combination at a proportion of 1% and 2%. Finally, specimens were tested in wet and dry conditions for each mix combination. During the triaxial testing phase, only the optimum bitumen content of 2.4% was used, both for bitumen emulsion and foamed bitumen, with only cement as active filler in a proportion 1% and 2%. The specimens were tested at different ranges of densities and saturation levels. The flexibility of the mix was assessed through the fracture energy, the strain and the displacement at break parameters. An analysis of variance (ANOVA) was conducted on the data to assess the significance of experimental variables on this property. This property was found to be very sensitive to bitumen and cement content added to the mix. When assessing the combined effect and the significance of the variables on the flexibility of the mixes, it was found that fracture energy is mostly influenced by the cement content, followed by the bitumen content, then the type of treatment and finally the testing condition. However, the level of significance was not in the same order for the other two parameters (displacement and strain at break). It was also found that the combined effect of some independent variables (cement content + testing condition, type of treatment + cement content + bitumen content) had a significant effect on the fracture energy and the strain at break respectively. From the ITS and UCS tests, an increase in strength was noticed with the increase of cement content. On the other hand, the increase in bitumen content led to a decrease in strength of the material. The statistical analysis on the ITS and UCS values show that the independent variable with the most significant effect on the ITS is the cement content, followed by the testing conditions, then the bitumen content and finally the type of treatment. The combined effect of cement content + bitumen content was found to be significant both for ITS and UCS. In the second phase triaxial tests were performed in order to evaluate the performance properties of the mixes. It was found that the increase of the active filler content significantly improves the shear strength of the material. It was also found that at a fixed cement content, specimens tested at low density and/or high level of saturation show low shear strength. The Mr-θ model was used to model the resilient modulus of the mixes and the model coefficients used to evaluate the effect of experimental variables on the resilient modulus. It was found that the resilient modulus of the mixes increases as the bulk stress increases. This confirms the stress dependent behaviour of bitumen stabilised materials. The analysis show that increasing the percentage of active fillers content results in a significant increase in the resilient modulus values. An increase in relative density also resulted in an increase in the resilient modulus of the mixes, while the opposite effect was observed with the increased of the saturation level. Besides the engineering properties and the mechanical test parameters, other parameters such as the Tensile Strength Ratio (TSR) was calculated in order to evaluate the moisture sensitivity of the mixes. Weakening due to moisture was found to be more predominant in the mixes with less active filler. In addition, bitumen emulsion mixes were found to have a better resistance to moisture weakening effects compared to foamed bitumen. In addition, a comparison between the rapid curing and the accelerated curing was done. Higher ITS and UCS results were obtained for specimens cured using long term curing compared to specimens cured using the accelerated curing method. In conclusion, flexibility is an important property of bitumen road construction material (bitumen stabilised material include) however, it is not an easy property to measure. Although, displacement/strain at break and fracture energy from ITS and UCS were able to give us some indications on the main factors governing the flexibility of bitumen stabilised materials (the bitumen and active filler content), more accurate and adequate tests are required to evaluate the parameter. / AFRIKAANSE OPSOMMING: Die buigsaamheid en gedragseienskappe van bitumen gestabiliseerde materiale was getoets om sodoende die invloed van verskeie mengselveranderlikes te evalueer. Die ondersoek het uit twee fases bestaan. Tydens die eerste fase (mengfase) is die sterkte en buigsaamheid deur middel van indirekte treksterkte toetse (ITS), onbegrensde druksterkte toetse (UCS), verplasing – en vervorming by breekpunt sowel as breek-energie toetse gedoen en ondersoek. Die tweede fase het bestaan uit ʼn reeks drie-assige triaksiaal toetse. Triaksiaaltoetse is uitgevoer om die gedragseienskappe soos die skuifsterkte, kohesie, hoek van interne wrywing, styfheid en weerstand modulus te ondersoek. Die gemaalde mineraal-aggregaat wat in hierdie ondersoek gebruik is, was verkry op verskeie areas van die R35, geleë naby Bethal. Die materiaal is ʼn mengsel van granulêre materiaal (van die bestaande kroonlaag en stutlaag van die pad) en herwonne asfalt (RA). Tydens die mengontwerp fase is twee tipes bitumen gebruik naamlik bitumenemulsie en skuimbitumen in hoeveelhede van 2%, 2.4% en 2.8%. Twee tipes aktiewe vulstof (hoeveelhede van onderskeidelik 1% en 2%) was saam met elk van die verskeie bitumen-hoeveelhede gebruik. Proefstukke van elk van hierdie mengsel kombinasies is onder beide nat en droë kondisies getoets. Tydens die tweede fase, is slegs die optimum binder inhoud (2.4%) gebruik vir beide emulsie- en skuimbitumen, gekombineer met 1% en 2% aktiewe vulstof. Proefstukke was getoets by ʼn reeks van verskillende digthede en versadigingvlakke. Die buigsaamheid was ondersoek deur middel van breek-energie, vervorming en die verplasing by breekpunt. ʼn Analise van variasie (ANOVA) is uitgevoer op die toetsdata om sodoende die te evalueer of die veranderlikes beduidend is ten opsigte van buigsaamheid. Daar is gevind dat die buigsaamheideienskap sensitief is vir beide bitumen en sement inhoud. Met assessering van die gekombineerde effek en betekenis van die veranderlikes op die buigsaamheid van die mengsels, is daar gevind dat die hoogste beduidende veranderlike t.o.v breek-energie die sement inhoud is, gevolg deur die bitumeninhoud, tipe behandeling en laastens die toetskondisie. Die orde van belangrikheid verskil vir die ander twee parameters (verplasing en vervorming by breekpunt). Daar is ook gevind dat die gekombineerde effek van sommige veranderlikes (sement inhoud en toets kondisie, tipe behandeling en sement inhoud tesame met bitumen inhoud) ook beduidend was t.o.v breek-energie en vervorming by breekpunt. Vanuit die ITS en UCS toetse was daar ʼn toename in sterkte waargeneem soos die sementinhoud toeneem. Aan die anderkant, het ʼn toename in bitumeninhoud ‘n afname in sterkte veroorsaak. Die statistiese analise van ITS en UCS resultate, toon dat die grootste beduidende onafhanklike t.o.v ITS waardes ook die sement inhoud was, gevolg deur toets kondisies die grootste effek, bitumen inhoud en die tipe behandeling. Die gekombineerde effek van sementinhoud en bitumeninhoud, was betekenisvol vir beide ITS en UCS. Drie-assige triaksiaaltoetse was uitgevoer om die gedragseienskappe van die mengsels te evalueer. Daar is gevind dat die toename in sement inhoud, die skuif sterkte van die materiaal grootliks verbeter. By ʼn konstante sementinhoud, wys toetsresultate van proefstukke wat getoets is by lae digthede en hoë vlakke van versadiging, lae skuif sterkte. Die Mr – θ model was gebruik om die veerkragsmodulus van die mengsels te moduleer en die modelkoëffisiënte is gebruik om die effek van eksperimentele veranderlikes op die weerstand modulus te evalueer. Met toename in die omhullende spanning is ‘n toename in die veerkragsmodulus waargeneem, wat bevestig dat die gedrag van bitumen gestabiliseerde materiale spannings afhanklik is. ʼn Toename in die sement en relatiewe digtheid het ʼn merkwaardige toename in die veerkragsmodulus tot gevolg gehad, terwyl die teenoorgestelde waargeneem is met toename in versadigingsvlakke. Buiten die ingenieurseienskap en meganiese toetsfaktore, is ander faktore (soos die trekspanning verhouding) bereken om die vogsensitiwiteit van die mengsels te evalueer. Mengsels met laer sement inhoud het groter verswakking ervaar met blootstelling aan water. Bitumenemulsie proefstukke toon beter weerstand teen water as skuimbitumen. Vergelyking tussen versnelde en korttermyn nabehandelingsprosedure van proefstukke, toon hoër ITS en UCS waardes vir die versnelde nabehandelingsprosedure prosedure. Buigsaamheid is ‘n belangrike eienskap van bitumen in padkonstruksie materiale (insluitend bitumen gestabiliseerde materiale), maar word moeilik gemeet. Alhoewel verplasing/vervorming by breekpunt en breek energie, bepaal vanaf ITS en UCS, ‘n indikasie toon van die hooffaktore (binder en sement) wat buigsaamheid van bitumen gestabiliseerde materiaal beïnvloed, word meer akkurate toetse benodig om die eienskap te ondersoek.

L’exploitation des ressources naturelles non conventionnelles en substitution du pétrole est un des défis du 21e siècle. La transformation microbiologique in situ de ces ressources en méthane est une des voies les plus prometteuses développées aujourd’hui mais son application reste à démontrer. Mes objectifs ont été de démontrer l'existence d'une conversion microbiologique en méthane de la matière organique (MO) de schistes immatures et de la quantifier pour extrapoler la production potentielle de méthane à l’échelle d’un bassin sédimentaire. Une méthode de détection et de suivi des consortia méthanogènes des schistes cartons en microcosmes, par une combinaison de PCR quantitative, GC-FID et pyrolyse Rock-Eval, a été mise au point et validée. Elle a été appliquée à l’étude de la distribution spatiale des méthanogènes dans les schistes cartons du bassin de Paris et à la démonstration de la méthanisation de la MO de ces roches. Les résultats montrent comme attendu la conversion des fractions solubles de la MO (bitume) par un consortium méthanogène isolé des schistes, mais également la transformation d’une fraction plus complexe (kérogène). L’absence de corrélation stricte entre la lithologie et la présence de méthanogènes actifs rend l’extrapolation au niveau du bassin plus difficile, mais la localisation des méthanogènes à la fois dans et hors les zones riches en MO constitue un avantage certain dans l'optique d'une exploitation économique de ces ressources. Ces travaux démontrent un potentiel élevé de production microbiologique de méthane dans le bassin de Paris et ouvrent la voie vers des études de faisabilité et rentabilité économique à l’échelle d’un site de production. / The exploitation of natural unconventional resources in substitution for petroleum is one of the challenges of the 21st century. In situ microbial transformation of these resources in methane is one of the most promising pathway currently developed, although its application needs to be demonstrated. My objectives were to demonstrate the existence of a microbial conversion into methane of the organic matter (OM) of immature shales, and to quantify it in order to extrapolate the potential for methane production of the rocks at the sedimentary basin scale. A method of detection and monitoring of methanogenic consortia from paper shales in microcosms, combining quantitative PCR, GC-FID and Rock-Eval pyrolysis, was developed and validated. It was used to study the spatial distribution of methanogens in paper shales of the Paris Basin and to demonstrate the methanization of the OM of these rocks. The results show the conversion of the soluble fractions of the OM (bitumen) by methanogenic consortia isolated from shales, but also the transformation of a more complex fraction (kerogen). No strict correlation was established between lithology and presence of active methanogens, which makes the extrapolation of methane production to the basin scale more difficult. However, the localization of methanogens in both OM-rich and OM-poor zones constitute an advantage in the perspective of an economic exploitation of these resources. This work demonstrates a great potential for microbial methane production in the Paris Basin and paves the way to studies of economic feasibility and profitability on the scale of a production site.

Les matériaux de chaussée dits “à froid”, formés d’un mélange de granulats et d’une émulsion de bitume, constituent une alternative plus économique et respectueuse de l’environnement aux matériaux de chaussée classiques. Cependant, ces mélanges incorporent une quantité significative d’eau, retardant la consolidation du mélange granulaire. L’objectif de cette thèse est de comprendre le déroulement du séchage au sein de l’enrobé, un milieu granulaire poreux saturé en émulsion de bitume, et quel en est l’effet sur sa structure et ses propriétés. Les principaux mécanismes du séchage de milieux poreux simples initialement saturés en eau sont relativement bien connus : celui-ci se déroule selon une longue première période à vitesse constante associée à une désaturation homogène du milieu et durant laquelle environ 90% d’eau est extraite, suivie d’une période à vitesse décroissante. Quelques travaux ont récemment montré que l’on peut largement s’éloigner de ce schéma dès que le fluide interstitiel est plus complexe (solution saline, suspension, gel), du fait du transport et/ou de l’accumulation des composants non-évaporables contenus dans le fluide. Nous avons choisi de décomposer le problème en étudiant d’abord le séchage du fluide complexe seul, autrement dit l’émulsion de bitume (ainsi que des émulsions modèles de silicone afin de mieux comprendre les mécanismes), puis le séchage de cette même émulsion en milieu poreux. Notre travail s’appuie sur le suivi « macroscopique » du séchage (i.e. pesée), et un suivi des caractéristiques internes (distribution de de liquide au sein du matériau) par Imagerie par Résonance Magnétique, qui fournit des informations originales très complètes. Nous montrons ainsi que l’extraction d’eau résultant du séchage d’émulsions modèles de silicone et de bitume seules est essentiellement homogène sur toute l’épaisseur (centimétrique) de l’émulsion, et associée à la compaction et la déformation progressives des gouttes de phase dispersée. Cependant, un gradient de concentration existe près de la surface libre et il s’avère que dans cette zone la coalescence de gouttes de phase dispersée ralentit très fortement le séchage. Nous montrons ensuite que la vitesse de séchage de milieux poreux initialement saturés en émulsion diminue dès le départ et continuellement jusqu’à de très faibles valeurs. La formation et la progression rapide d’un front sec dans le milieu poreux ainsi que l’absence de migration de bitume dans le milieu poreux, observés par IRM, permettent d’expliquer en partie ce phénomène, mais il faut probablement y ajouter les caractéristiques propres du séchage de l’émulsion de bitume, qui contribuent également à ralentir la vitesse d’évaporation / The preparation of cold mix asphalts, composed of aggregates and bitumen emulsion, represent a substantial economic and environmental potential but the presence of water delays the strengthening of the material. Our objective is to understand how the mix dries and how this affects its properties. The drying of pure liquids in simple porous media has been extensively studied : a constant drying rate period as well as a homogeneous distribution of water are observed until 90% of the water has been extracted; afterwards the drying rate decreases. Studies have shown that the drying of complex fluids (ionic solutions, suspensions, gels) is very different due to the transport and/or accumulation of the fluid’s non-vaporizable elements. We chose to study first the drying of the complex fluid i.e. the bitumen emulsion as well as silicone oil emulsions to understand better the drying mechanisms, then the drying of the complex fluid in a porous media. We used Magnetic Resonance Imaging (MRI) to monitor the internal characteristics of our systems. This allowed us to show that water is extracted uniformly over the drying emulsion’s entire thickness ($approx$cm), leading to the progressive droplet compaction and deformation. However, a water concentration gradient forms near the free surface, which ultimately slows the drying as droplets coalesce. We then show that the drying rate of a porous medium initially saturated with emulsion decreases from the beginning of drying. The rapid formation and progression of a dry area in the porous medium and the absence of bitumen transport partly explain this but it is very likely that the bitumen emulsion’s drying characteristics contribute to the decreasing drying rate

The main objective of this research was to exploit the interrelations between the rheological behavior and nano-microstructure of complex fluids in solving two state-of-the-art problems, one in the field of biomedical engineering: controlling the amount and characteristics of bioaerosol droplets generated during coughing, and the other in the bitumen-heavy oil industry: characterizing the nano-microstructure of asphaltene particles in bitumen and heavy oil from their rheological behavior. For the first problem, effect of viscoelastic and surface properties of artificial mucus simulant gels on the size distribution and amount of airborne bioaerosol droplets generated during simulated coughing were investigated. The results revealed that suppressing the generation of bioaerosol droplets and/or reducing the number of emitted droplets to a minimum during coughing are practically achievable through modulation of mucus viscoelastic properties. While variation of surface tension did not show any change in the droplet size distribution, an increase in particle size was observed as the samples changed from elastic solid type to viscoelastic type to viscous fluid type samples. This knowledge will help in the development of a new class of drugs being developed at the University of Alberta, aimed at controlling the transmission of airborne epidemic diseases by modifying the viscoelastic properties of mucus. For the second problem, studies of viscoelastic behavior of Athabasca bitumen (Alberta) and Maya crude (Mexico) oil samples, along with their Nano-filtered and chemically separated-plus-reconstituted samples were performed. The results revealed that the rheological behaviors of the bitumen-heavy oil samples are governed by their multiphase nature. The rheological behavior of all feeds, permeates and retentate samples followed a single master curve over the entire temperature interval, consistent with that of a slurry comprising a Newtonian liquid plus a dispersed solid comprising non-interacting hard spheres. The behavior of asphaltenes in the reconstituted samples, however, was found to be significantly different from that in nanofiltered samples. The information about the characteristics and behaviors of asphaltenes obtained in this study will help better understand the asphaltene structures, and support the effort to determine solutions for numerous asphaltene-related industrial problems. In the long run, this knowledge will help to create more efficient extraction and upgrading processes for bitumen and heavy oils. / Thermo Fluids

Phase behaviour information is essential for the development and optimization of hydrocarbon resource production, transport and refining technologies. Experimental data sets for mixtures containing heavy oil and bitumen are sparse as phase behaviour data are difficult to obtain and cost remains prohibitive for most applications. A computational tool that predicts phase behaviours reliably for mixtures containing such ill-defined components, over broad temperature, pressure and composition ranges would play a central role in the advancement of bitumen production and refining process knowledge and would have favourable impacts on the economics and environmental effects linked to the exploitation of such ill-defined hydrocarbon resources. Prior to this work, predictive computational methods were reliable for dilute mixtures of ill-defined constituents. To include a much wider range of conditions, three major challenges were addressed. The challenges include: creation of a robust and accurate numerical approach, implementation of a reliable thermodynamic model, and speciation of ill-defined constituents like Athabasca Bitumen Vacuum Residue (AVR). The first challenge was addressed by creating a novel computational approach based on a global minimization method for phase equilibrium calculations. The second challenge was tackled by proposing a thermodynamic model that combines the Peng-Robinson equation of state with group contribution and related parameter prediction methods. The speciation challenge was addressed by another research group at the University of Alberta. Pseudo components they proposed were used to assign groups and estimate thermodynamic properties. The new phase equilibrium computational tool was validated by comparing simulated phase diagrams with experimental data for mixtures containing AVR and n-alkanes. There is good qualitative and quantitative agreement between computed and experimental phase diagrams over industrially relevant ranges of compositions, pressures and temperatures. Mismatch was only observed over a limited range of compositions, temperatures and pressures. This computational breakthrough provides, for the first time, a platform for reliable phase behaviour computations with broad potential for application in the hydrocarbon resource sector. The specific computational results can be applied directly to solvent assisted recovery, paraffinic deasphalting, and distillation and refining processes for Athabasca bitumen a strategic resource for Canada. / Chemical Engineering

This report offers a comparative valuation of two bitumen production technologies, using real options analysis (ROA) techniques to incorporate strategic flexibility into the investment scenario. By integrating a probabilistic cost model into a real options framework, the value of an oil recovery facility is modeled to reflect the realistic alternatives available to decision-makers, where the course of the investment can be altered as new information becomes available. This approach represents a distinct advantage to traditional discounted cash flow (DCF) estimation, which is unable to capture operational adaptability, including the ability to expand, delay, or abandon a project. The analysis focuses on the energy inputs required for the recovery of heavy oil bitumen from Alberta, Canada, and examines both natural gas and nuclear steam plants as heat sources. The ACR-1000 reactor is highlighted as a substitute for conventional natural gas-fueled means of production, in light of the recent volatility of natural gas prices and the potential for emissions compliance charges. The methodology includes a levelized cost assessment per barrel of bitumen and estimation of cost ranges for each component. A mean-reversion stochastic price model was also derived for the both natural gas and oil price. By incorporating cost ranges into a ROA framework, the benefit of retaining project flexibility is included in its valuation. Formulated as a decision tree, built-in options include the initial selection to pursue nuclear or natural gas, site selection and licensing, the ability to switch heat source in the planning stage, and the final commitment to construct. Each decision is influenced by uncertainties, including the course of bitumen and natural gas price, as well as emissions policy. By structuring the investment scenario to include these options, the overall value of the project increases by over $150 million. The ability to switch technology type allows for an assessment of the viability of nuclear steam, which becomes economically favorable given high natural gas prices or high emissions taxes. Given an initial selection of natural gas SAGD, there is a 25% probability that a switch to nuclear steam will occur, as evolving financial conditions make nuclear the optimal technology. / text