abstract: Bio-modification of asphalt binder brings significant benefits in terms of increasing sustainable and environmental practices, stabilizing prices, and decreasing costs. However, bio-modified asphalt binders have shown varying performance regarding susceptibility to moisture damage; some bio-oil modifiers significantly increase asphalt binder's susceptibility to moisture damage. This variability in performance is largely due to the large number of bio-masses available for use as sources of bio-oil, as well as the type of processing procedure followed in converting the bio-mass into a bio-oil for modifying asphalt binder. Therefore, there is a need for a method of properly evaluating the potential impact of a bio-oil modifier for asphalt binder on the overall performance of asphalt pavement, in order to properly distinguish whether a particular bio-oil modifier increases or decreases the moisture susceptibility of asphalt binder. Therefore, the goal of this study is a multi-scale investigation of bio-oils with known chemical compositions to determine if there is a correlation between a fundamental property of a bio-oil and the resulting increase or decrease in moisture susceptibility of a binder when it is modified with the bio-oil. For instance, it was found that polarizability of asphalt constituents can be a promising indicator of moisture susceptibility of bitumen. This study will also evaluate the linkage of the fundamental property to newly developed binder-level test methods. It was found that moisture-induced shear thinning of bitumen containing glass beads can differentiate moisture susceptible bitumen samples. Based on the knowledge determined, alternative methods of reducing the moisture susceptibility of asphalt pavement will also be evaluated. It was shown that accumulation of acidic compounds at the interface of bitumen and aggregate could promote moisture damage. It was further found that detracting acidic compounds from the interface could be done by either of neutralizing active site of stone aggregate to reduce affinity for acids or by arresting acidic compounds using active mineral filler. The study results showed there is a strong relation between composition of bitumen and its susceptibility to moisture. This in turn emphasize the importance of integrating knowledge of surface chemistry and bitumen composition into the pavement design and evaluation. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2020

In this Study, the surface energy was investigated for six penetration grade 70/100 bitumen binders. Wilhelmy Plate and the Sessile Drop were used to determine the contact angles. The purpose of this study was to compare the Wilhelmy Plate method with the Sessile Drop method, and to compare the significance of Owens-Wendt model with the significance of Acid Base model by correlating surface energy components. Better R2 –values were found for surface energy components by using the Owens-Wendt model than by using the Acid Base model. It was concluded here that Owens-Wendt model is a better model for determining surface energy components of bituminous binders than the Acid Base model since bituminous binders have low energy surfaces. For both instruments: When using Diiodomethane as a probe liquid the biggest variations among the binders were observed. When using water as a probe liquid the least variations among the binders were observed. The advancing contact angles for water determined for these six bitumen binders using the Wilhelmy plate method do not exceed the 90 degree by much, suggesting that bitumen is not extremely hydrophobic. The Sessile Drop method offers a faster and more convenient way to measure the surface energy components of bitumen binders than the Wilhelmy Plate method.

In this thesis, a review is given on the most popular polymers used today for polymer modification of bitumen. Furthermore, the development of a model for phase separation in polymer modified bitumen (PMB) is proposed, that will enable a better control and understanding of PMB phase behaviour, allowing thus to enhanced long-term performance. PMB is hereby considered as a blend and focus is placed on its structure, its equilibrium thermodynamics and its phase separation dynamics. The effects of dynamic asymmetry on phase separation in PMB are analysed with related theories and some image data. Based on the discussion in this thesis, it is concluded that the effects of dynamic asymmetry between bitumen and polymer should be taken into consideration when studying phase separation in PMB. By analysing related literature and image data, it is found that some features of viscoelastic phase separation are shown during the phase separation process in some PMBs. It is therefore possible and useful to develop a viscoelastic model for PMB to describe its phase separation behaviour. In this, the stress-diffusion coupling is expected to play a key role in the model. Finally, recommendations are made towards the future research which is needed to realize the proposed model. / <p>QC 20150409</p>

The environmental processes and conditions controlling productivity and organic matter (OM) accumulation/preservation as well as bottom–water redox conditions in the lower black shale (LBS) and upper black shale (UBS) members of the Devonian-Mississippian (D–M) Bakken Formation were evaluated utilizing trace metal (TM) concentrations, degree of pyritization (DOPT), enrichment factors (EF) of TMs, bi–metal ratios (V/Cr, V/(V+Ni), Ni/Co, U/Th), total sulfur (ST) vs. iron (Fe), total organic carbon (TOC), carbon–sulfur–iron relationships (C–S–Fe), as well as Mo–TOC and Mo EF–U EF relationships. High-resolution (1- to 3-cm scale) chemostratigraphic records were generated for twelve drill cores, four of which closely flank the N–S-trending axis of the Nesson Anticline, proximal to the center of the Williston Basin in northwest North Dakota, USA. Furthermore, five of the twelve drill cores were selected (sample selection was based on down–core spacing and TM concentrations) for petrographic and Rock-Eval analysis to assess variations in kerogen type, quantity, quality, and thermal maturity (based on solid bitumen reflectance (%SBRo), vitrinite reflectance equivalence (%VRE), Rock–Eval Tmax–derived vitrinite reflectance (%Ro)) from immature to condensate, wet gas hydrocarbon generation windows. Degree of pyritization (DOPT) values (0.25 to 1.0) indicate that bottom waters were frequently dysoxic (> 60%) with intermittent aerobic and anoxic/euxinic conditions which is in agreement with C–S–Fe and total ST vs. Fe assessments of paleoredox conditions and sedimentological evidence. Furthermore, using published Mo–TOC relationships from modern anoxic-euxinic basins, it is estimated that renewal time of the sub-chemoclinal water mass during accumulation of the LBS and UBS approximated 10 and 30 yrs., respectively. Agreement is also seen between Mo/TOC and Mo EF/U EF where both suggest the Bakken shales were deposited under relatively unrestricted water mass conditions resulting in consistent renewal of TMs into the basin. However, bi–metal ratios suggest > 80% of samples were deposited under suboxic to anoxic/euxinic conditions. Trace metal concentrations for the Bakken Fm. show considerable range for Co (0–10324 ppm), Mo (0–2018 ppm), Ni (0–1574 ppm), U (0–1604 ppm), and V (0–3194 ppm), and bi–metal ratios for the Bakken Fm. are up to 5x greater than those reported for other D–M black shale formations. The Bakken black shales represent a unique sedimentary system where the EF of various TMs such as Cu (6.2–7.7), Mo (219.7–237.8), Ni (9.4–10.2), U (20.6–29.3), V (9.9–14.2), and Zn (10.4–12.2) as well as total organic carbon contents (LBS = 10.80 and UBS = 11.80 avg. wt.%) are considerably higher than other Devonian–Mississippian black shales. In this study, raw distributions of elemental concentrations combined with bivariate and principal component analysis (PCA) were used to elucidate the processes that could have contributed to the high EF of TMs in the Bakken shales. Total organic carbon shares heavier PCA component loadings (>0.445) and stronger correlation coefficients (r) with Cu, Mo, Ni, U, V, and Zn rather than with pyrite-associated (As, Co, Fe, and S) elements, suggesting that TOC played a primary role in the scavenging and accumulation of TMs in the sediments. Reducing conditions within bottom waters or sediment pore waters may have accelerated the accumulation of redox-sensitive Cu, Mo, Ni, V, and Zn introduced into the sediments via primarily an organic matter (OM) detritus host and most likely played a secondary role in the enrichment of TMs. The high EF of TMs observed in the Bakken shales may be the result of the frequent resupply of TMs into basin waters, enhanced primary productivity that is necessary in scavenging TMs from the water column, the presence of H2S within sediment pore or bottom waters, or possibly secondary processes associated with basin-wide fluid and hydrocarbon migration. Factors controlling TM accumulation during time of deposition (e.g., TM availability, bottom-water redox conditions, adsorption onto organic matter) and during diagenesis and catagenesis (e.g., alteration and break down of organic matter, movement of fluid hydrocarbons or other basinal fluids) likely contribute to the lack of agreement between redox proxies, and subsequently, the lack of applicability of bi–metal ratios (i.e., V/Cr, V/(V+Ni), Ni/Co, U/Th) in assessing bottom–water conditions for the Bakken shales. Solid bitumen (SB), a secondary organic matter formed as a residue after hydrocarbon generation (through either sufficient thermal maturation or microbial degradation) and expulsion, is primarily dispersed within the mineral matrix and increases in quantity with increasing thermal maturity. Rock-Eval II and HAWK analyzers were used to measure and estimate the hydrogen index (HI; avg. 201 mg HC/g TOC), oxygen index (OI; avg. 7mg CO2/g TOC), S1 (free hydrocarbons; avg. 8.0 mg HC/g rock), S2 (hydrocarbons generated after cracking kerogen; avg. 24.3 mg HC/g rock), and %Ro (0.60–1.03%; estimated from Tmax). The HI and OI values are calculated from TOC as well as S2 and S3 (oxygen bonded to hydrocarbons). Plots of HI vs. Tmax (ºC) and HI vs. OI as well as S2 vs. S3 ratio were utilized to determine the type of kerogen, primary OM that is insoluble in organic solvents. However, these relationships are not in agreement with kerogen typing based on petrographic observations, where samples from more thermally mature cores plot as Type III (vitrinite) kerogen instead of observed Type I/II (marine algae) kerogen. This is largely due to the abundant presence of SB in the more thermally mature section of the Bakken (Rock-Eval Ro = 0.83–1.03%) as SB is known to have a lower HI content than Type II kerogen. Petrographic evidence shows greater abundance of alginite and amorphous organic matter (AOM or bituminite) in the thermally less mature (Rock-Eval Ro = 0.60–0.83%) section of the Bakken compared to the greater abundance of dispersed SB in the more thermally mature section where AOM is absent. Early research on the Bakken Fm. reported lower than expected vitrinite reflectance values attributed to vitrinite “suppression". The overall lack of vitrinite and abundance of solid bitumen in these shales suggests that these early attempts likely reported solid bitumen reflectance rather than vitrinite reflectance. More recent attempts to assess the thermal maturity of the Bakken Fm. black shales have measured and converted SBRo to vitrinite reflectance equivalent (VRE). However, samples selected for SBRo by some previous workers have included heterogenous, granular as well as high reflecting SB samples, which introduce error in the measurements. As such, reported reflectance values are most likely lower than they would be if smooth, homogenous solid bitumen with no inclusions were measured. For this project, smooth and homogenous SB was measured to produce consistent and reliable VRE values to assess the thermal maturity gradient from the Bakken Fm. basin margins to the depocenter. Blue-light fluorescence petrography was done to support thermal maturity assessments. Results from SBRo, Rock-Eval Ro, VRE, and blue-light fluorescence observations suggest that cores from the current study range from early oil window into condensate, wet gas.

No description available.

Detta examensarbete utfördes hos Skanska Industrial Solutions (SIS) och syftade till att undersöka sätt att minimera koldioxidutsläppen från Skanskas asfaltproduktion genom optimering. En icke-linjär optimeringsmodell utvecklades för att beräkna den optimala inblandningen av jungfruliga material och returasfalt samt mängden årston som ska produceras för att minimera koldioxidutsläppen per ton tillverkad asfalt. Utgångspunkten för modellen var att på ett så verklighetstroget sätt som möjligt beskriva de olika aspekterna i asfaltproduktionens utsläpp. Modellen tar hänsyn till begränsningar såsom maximal tillåten inblandning av returasfalt, maximal produktionsnivå och tillgången på returasfalt. El- och biooljeförbrukningen modellerades som funktioner av produktionsvolymen genom minsta kvadratmetoden för att beskriva hur förbrukningen förändrades i takt med en ökad mängd producerad årston. Resultaten visar att en hög inblandning av returasfalt är den viktigaste faktorn för att minska koldioxidutsläppen. Modellen visade också att mängden årston har en inverkan på koldioxidutsläppen per ton tillverkad asfalt där en högre produktion leder till lägre utsläpp per ton. En undersökning av framtida scenarion med en lägre tillgång på returasfalt visade dock att mängden årston endast bör ökas så länge en maximal inblandning av returasfalt fortfarande är möjlig.

La croissance de caution vis-à-vis l'utilisation des produits pétroliers dans la construction a nécessité le besoin de développement des alternatives. Le BTP, en particulaire pour le secteur routière, a un certain nombre des piste ou les produits pétrolières ont utilisés, par exemple le liant pour les enrobés comme les agents régénérant (pour recyclage des enrobés), mais aussi le produits qui sont utilisés sur le chantier comme les anti-adhérents (ARA) et les débituminants (BR). Alors, il y a une besoin de remplacer les produits d'origines pétrolières par les alternatives bio-sourcés. Ce présent ouvre est une partie d'un projet qui va développer une nouvelle filière dédiée à la production de nouvelles formulations pour le BTP à partir de la transformation des huiles végétales et des graisses animales. Ce thèse concerne les produits développés seront destinés au l'asphalte, et alors, deux types d'applications sont particulièrement visés : (i) des agents anti-adhérents et (ii) des agents régénérants. Un débituminant sera développé aussi. Les produits anti-adhérents ont pour fonction d'empêcher le bitume d'adhérer aux engins de travaux sans effet secondaire, théoriquement, sur la matrice liante.. L'objet du travail est de caractériser l'efficacité et l'innocuité des agents anti-adhérents développés dans le cadre du projet et de développer les méthodes expérimentales visant à les évaluer. Trois essais principaux ont été développés pour caractériser la performance et innocuité des anti-adhérents vis-à-vis des essais qui ont optimisé leur implémentation et paramètres. La performance des anti-adhérents a été caractérisé par l'essai de glissance des enrobés. L'innocuité des anti-adhérents ont été caractérisés par des essais de fendage sur les enrobés et par l'essai de la dégradation de bitume. L'essai de la dégradation de bitume a servi aussi comme une mesure de la performance de débituminant. Les essais sur les anti-adhérents commerciaux d'Etats-Unis et la France a trouvé que ils ont deux modes de fonctionnement : i) lixiviation du bitume et ii) en formation d'une interface entre le les enrobés et la surface métallique. Même comme les deux modes ont été trouvé dans des certains anti-adhérents, le mode interface ont été trouvé préférable, grâce à l'option de garder les mêmes applications du produit pour plusieurs cycles de usage. Ensuite, un produit - basé sur glycérol sourcé de l'agro-industrie - a été développé. Les débituminants commerciaux ont été essayé, aves les conclusions : i) les débituminants plus effectifs ont eu les plus grande % des esters et ii) que les esters chaines courtes (C7-10) d'hautes concentrations ont été trouvé les plus efficace. L'agent régénérant est destiné à régénérer le bitume vieilli issu des agrégats d'enrobés (RAP) en lui redonnant ses propriétés originelles et en assurant leur maintien dans le temps. Le travail sur les agents régénérants se compose de la caractérisation physico-chimique du vieillissement du bitume et du bitume vieilli avec l'agent. Plus précisément, le travail se serve des techniques de spectrométrie IRTF (avec imagerie) et thermogravimétrie. Dans ce contexte, une produit bio-sourcé a été évalué comme une régénérant. Pour la spectroscopie FTIR, une moyenne de polir le mastique a été développé pour rassuré la platitude des échantillons. La régénération du bitume a été observé avec la spectrométrie ITRF, donc quelques peaks (notamment les indices IC=O and IS=O) pendant 0-42 jours de vieillissement dans l'étuve (loin-durée). Il a été trouvé qu'une période de vieillissement de 14 jours à l'étuve était à peu près équivalente au bitume vieilli par un cycle de RTFOT + PAV en termes de rhéologie et de la pénétration. Le mastic (vieilli 14 jours) a ensuite été mélangé avec un agent de bio-source (à 7,5% en poids de mastic). Il a été constaté par imagerie FTIR que l'indicateur de l'oxydation IS=O a été réduit par l'incorporation de l'agent régénérant dans le bitume. / The growing health and environmental concerns brought on by the use of petroleum based products in the asphalt construction industry have necessitated the development of alternatives. Infrastructure, especially that involving transportation has many uses for petroleum products including, as fuel, as well as in asphalt pavement construction - where petroleum products have traditionally constituted the binder for the mix as well as the rejuvenating agents (for asphalt recycling) - along with various agents used in the construction process including bitumen removers and asphalt release agents. Thus, there is a need to replace petroleum base agents with bio-sourced and biodegradable substitutes. The present work is part of a project to develop bio-sourced (recycled from agricultural waste) products for the construction industry. This work is dedicated to developing products relating to the asphalt industry. Two types of product applications were envisioned: i) an asphalt release agent (ARA) and ii) an asphalt rejuvenating agent. Additionally, a bitumen remover (BR) developed as part of the work on the ARA. ARAs prevent asphalt from adhering to tools and equipment used in asphalt production, without producing overly negative side effects with regards to the pavement. Three principal tests methods were developed and optimized for the performance and damage to asphalt of the ARAs. The asphalt slide test was developed to quantify the performance of the ARA by sliding hot asphalt mix down a plate with the ARA applied. The testing of the damage to asphalt from ARAs consisted of testing an asphalt cylinder - in contact with an ARA for seven days - in indirect-tensile strength (ITS). The bitumen degradation test consisted of submerging a bitumen sample in an agent over a certain time and weighing the bitumen that did not dissolve in the agent. This was followed by the observation of the bitumen-ARA chemical interaction by FTIR spectrometry. This test served as an assessment of ARA damage to bitumen as well as of the performance of BRs. The testing of the commercial ARAs from both the French and USA markets found that they had two primary modes of functioning: i) by softening the bitumen and ii) by forming an interface between the asphalt and the metal surface. While some agents had elements of both, it was found that interface agents are preferable, due to the ability to use a single ARA application for multiple occasions. With this completed, a water-based bio-sourced substrate ARA - based on glycerol derived from agricultural waste - was developed. The commercially available BRs were tested as well, finding that i) the most effective BRs had the highest ester concentration and ii) that highly concentrated short chained ester (C7-10) were very effective bitumen dissolvers. The goal of rejuvenating agents is to regenerate the old bitumen from recycled asphalt pavement (RAP) by restoring the original properties and ensuring the stability of these properties over time. This part consisted of the development of methods for bitumen and aging, as well as characterization of the chemical rejuvenation of bitumen by FTIR spectrometry (including imaging) and thermogravimetric analysis. A bio-sourced rejuvenating agent was evaluated as well. For the imaging, a mastic polishing method was developed in order to attain as samples as flat as possible for the analysis. The bitumen rejuvenation was observed using FTIR spectroscopy analysis. Several peaks (notably IC=O and IS=O) were observed for bitumen oven aged up to 42 days (long term). It was found that an oven aging period of 14 days was roughly equivalent to bitumen aged by a RTFOT+PAV cycle it terms of rheology and penetration. The mastic (aged for 14 days) was then combined with a bio-sourced agent (at 7.5%w of mastic). It was found by FTIR imaging that the oxidation indicator IS=O, was reduced by the incorporation of the rejuvenating agent.

The comparison of rheological properties (complex shear modulus and phase angle and dynamic viscosity) of four paving bitumens and two polymer modified bitumens is performed in this diploma thesis. Furthermore, the empirical tests (needle penetration and softening point) were determined on these binders. Effect of asphalt binders aging was modeled using RTFOT test and modified RTFOT test (3 x RTFOT).

This master's theseis deals with comparison of two design concepts for producting asphalt mixture with CRmB. These design concepts are from Sweden and USA. The theoretical part sets parameters for design of asphalt mixture and chracteristic tests. In the practical part test speciements of design asphatl mixture undergo performace tests that simulate climate and traffic load. Results are compared to mathematical model used in program LayEps.

The asphalt mixture BBTM 5 A with crumb rubber modified bitumen (CRmB) is designed and produced in the diploma thesis. The influence of CRmB content on low temperature properties, stiffness and fatigue of asphalt mixture BBTM 5 A is determined. The influence of asphalt mixture ageing simulation on change of low temperature properties is also evaluated.