Amorphous calcium carbonate (ACC) precipitation is modeled using particle nucleation, growth, and aggregation. The particles are tracked in terms of their radial size and particle density using direct quadrature method of moments (DQMOM). Four separate nucleation models are implemented and are compared to experimental data. In discord with a recent study, it is shown that classical nucleation, coupled with equilibrium chemistry, is in good agreement with experimental data. Novel nucleation mechanisms are presented which fit the experimental data with slightly greater accuracy. Using equilibrium chemistry it is shown that the equilibrium value of ACC is pKeq = 7.74 at 24C, which is a factor of two smaller than the originally published equilibrium constant. Additionally, legacy equilibrium chemistry expressions are shown to accurately capture the fraction of calcium carbonate ions formed into ACC nano-clusters. The density, solubility, and water content of ACC are discussed in a brief review, finding that a wide variety of properties are reported in the literature. Based on literature findings, it is proposed that the broad variety of reported properties may be due to ACC having several unique thermodynamic states. Compelling evidence is presented exposing errors made by experimentalists studying the calcium carbonate system. The errors correct for mistakes of experimental kinetic data of the chemical-potential cascade of calcium carbonate due to the formation of meta-stable phases. Correlations are presented which correct for these mistakes. A time-scale analysis shows the overlapping of kinetic scales and mixing scales within the calcium carbonate system. The kinetic scales are based on classical nucleation theory, coupled with diffusion limited growth. The mixing scales were computed using one-dimensional turbulence (ODT).

Fuel cells are promising candidates for converting chemical energy into electrical energy. The Molten Carbonate Fuel Cell (MCFC) is a high temperature fuel cell that produces electrical energy from a variety of fuels containing hydrogen, hydrocarbons and carbon monoxide. Since the waste heat has a high temperature it can also be used leading to a high overall efficiency. Material degradation and the cost of the components are the problems for the commercialisation of MCFC. Although there are companies around the world starting to commercialise MCFC some further cost reduction is needed before MCFC can be fully introduced at the market. In this work, alternative materials for three different components of MCFC have been investigated. The alternative materials should have a lower cost compared to the state-of-the-art materials but also meet the life-time goal of MCFC, which is around 5 years. The nickel dissolution of the cathode is a problem and a cathode with lower solubility is needed. The dissolution of nickel for three alternative cathode materials was investigated, where one of the materials had a lower solubility than the state-of-the-art nickel oxide. This material was also tested in a cell and the electrochemical performance was found to be comparable with nickel oxide and is an interesting candidate. An inexpensive anode current collector material is also desired. For the anode current collector, the contact resistance should be low and it should have good corrosion properties. The two alternative materials tested had low contact resistance, but some chromium enrichment was seen at the grain boundaries. This can lead to a decreased mechanical stability of the material. In the wet-seal area, the stainless steel used as bipolar/separator plate should be coated. An alternative process to coat the stainless steel, that is less expensive, was evaluated. This process can be a suitable process, but today, when the coating process is done manually there seems to be a problem with the adherence. This work has been a part of the IRMATECH project, which was financed by the European Commission, where the partners have been universities, research institutes and companies around Europe. / QC 20101123

Recycled concrete aggregate (RCA) is often used as a replacement of virgin aggregate in road foundations (base course), embankments, hot-mix asphalt, and Portland cement concrete. However, the use of RCA in exfiltration drainage systems, such as French drains, is currently prohibited in many states of the U.S. The French drain system collects water runoff from the road pavement and transfers to slotted pipes underground and then filters through coarse aggregate and geotextile. The primary concerns with using RCA as a drainage media are the fines content and the precipitation of calcium carbonate to cause a reducing in filter fabric permittivity. Additional concerns include the potential for rehydration of RCA fines. The performance of RCA as drainage material has not been evaluated by many researchers and the limited information limits its use. A literature review has been conducted on the available information related to RCA as drainage material. A survey was issued to the Departments of Transportation across the nation in regards to using RCA particularly in French drains. Some state highway agencies have reported the use of RCA as base course; however, no state reports the use of RCA in exfiltration drainage systems. This thesis describes the investigations on the performance of RCA as backfill material in French drains. RCA was tested for its physical properties including, specific gravity, unit weight, percent voids, absorption, and abrasion resistance. RCA cleaning/washing methods were also applied to evaluate the fines removal processes. The potential for RCA rehydration was iv evaluated by means of heat of hydration, pH, compressive strength, and setting time. The permeability of RCA was tested using the No. 4 gradation. Long term permeability testing was conducted to evaluate the tendency for geotextile clogging from RCA fines. Calcium carbonate precipitation was also evaluated and a procedure to accelerate the precipitation process was developed. The results show that RCA has a high abrasion value, that is, it is very susceptible to break down from abrasion during aggregate handling such as transportation, stockpiling, or placing. The most effective cleaning method was found to be pressure washing with agitation. RCA has not demonstrated the tendency to rehydrate and harden when mixed with water. The permeability test results show that the No. 4 gradation does not restrict the flow of water; the flow rate is highly dependent on the hydraulic system itself, however excessive fines can cause large reductions in permeability over time. It has been determined that No. 4 gradation of RCA can provide a suitable drainage media providing the RCA is properly treated before its use.

The effects of global warming are well understood. In order to combat this, society must move towards net zero emissions of green house gases, where carbon dioxide (CO2) plays a key role. In several IPCC climate scenarios that meet the Paris agreement, negative emission technologies that effectively remove CO2 from the atmosphere are included. Of several different technologies, bioenergy with carbon capture and storage (BECCS) is one of the most mature. This technology utilises an absorption-desorption process where CO2 is solved in liquid, producing a rich solvent, and later desorbed, resulting in pure CO2. There are, however, still challenges to implement this technology on a large scale, and one such issue is the monitoring of process streams to gain control over process conditions and system parameters.  In this project, the absorption solvent in BECCS processes were mimicked in order to determine if FTIR spectroscopy could be used to produce process parameters that are accurate, sensitive and robust. Accuracy and sensitivity are defined as the ability to correctly predict the presence and amount of species of interest in the absorption liquid. Robustness on the other hand is defined as the ability to produce precise measurements in the presence of pollutants. To evaluate how accurate and sensitive the measurements are, two different numerical models were developed and calibrated using prepared samples mimicking an absorption solvent. One model was solely based on the least square method, whereas the other was based on principal component analysis (PCA). These models were then tested on clean validation samples, as well as pilot plant samples from Stockholm Exergi, in a case study. An analysis of FTIR spectra from simulated absorption liquids showed that it could distinguish between the species of interest. Furthermore, the spectra showed that pollutants did not impact the readings in a major way. The results showed that both models produced accurate predictions of process parameters.

A novel concept has been developed for the direct carbon fuel cell (DCFC) based on molten carbonate recirculating electrolyte. In the cathode, co-current flow of electrolyte with entrained gases carbon dioxide and oxygen is sent in the upward direction through a porous bed grid. In the anode, co-current flow of a slurry of electrolyte entrained with carbon particles is sent in the downward direction through a porous bed grid. The gases carbon dioxide and oxygen in the cathode react on the grid surface to form carbonate ions. The carbonate ions are then transported via conduction to the anode for reaction with carbon to produce carbon dioxide for temperatures under 750 deg C. A mathematical model based on this novel DCFC concept has been developed. The model includes governing equations that describe the transport and electrochemical processes taking place in both the anode and cathode and a methodology for solving these equations. Literature correlations from multi-phase packed-bed chemical reactors were used to estimate phase hold-up and mass transfer coefficients. CO production and axial diffusion were neglected. The results demonstrated that activation and ohmic polarization were important to the cell output. The impact of concentration polarization to the cell output was comparatively small. The bed depths realized were of the order of 10cm which is not large enough to accommodate the economies of scale for a large scale plant, however thousands of smaller cells (10 m^2 area) in series could be built to scale up to a 10 MW industrial plant. Limiting current densities of the order of 1000-1500 A/m^2 were achieved for various operating conditions. Maximum power densities of 200-350 W/m^2 with current densities of 500-750 A/m^2, and cell voltages of 0.4-0.5 V have been achieved at a temperature of 700 deg C. Over temperatures ranging from 700 to 800 deg C, results from the modeled cell are comparable with results seen in the literature for direct carbon fuel cells that are similar in design and construction. / Ph. D.

Yes / Cementitious composites are generally brittle and develop considerable tension cracks, resulting in corrosion of steel reinforcement and compromising structural durability. With careful selection and treatment, some kinds of bacteria are able to precipitate calcium carbonate and ‘heal’ cracks in cementitious composites through their metabolism, namely bacterial activity. It is envisioned that the bacterial technology-enabled cementitious composites could have great potential for engineering applications such as surface treatment, crack repair and self-healing construction material. This paper presents the state-of-the-art development of bacterial technology-enabled cementitious composites from the following aspects: mechanisms of bacterial induced calcium carbonate precipitation; methods of applying bacteria into cementitious composites; mechanical properties, durability and their influencing factors; various applications; cost effective analysis and prospect. The paper concludes with an outline of some future opportunities and challenges in the application of bacterial technology-enabled cementitious composites in construction. / National Science Foundation of China (51578110) and the Fundamental Research Funds for the Central Universities in China (DUT18GJ203).

Sub-seismic meter-scale interwell depositional facies heterogeneity and microporosity are critical components behind properties and fluid flow heterogeneities of many Middle eastern giants and supergiants carbonate reservoirs. The Hanifa reservoir is one of the most petroliferous Arabian carbonate strata that hosts the notoriously heterogenous stromatoporoid/coral facies. Paradoxically, the 3D geometry, architecture, and subsurface implication of these facies are poorly understood or completely ignored in most studies. The lower part of the Arab-D reservoir is dominated by microporosity. However, studies that investigate the influence of microcrystals that host microporosity to petrophysical properties and upscale it to reservoir simulation grid-block scale are modicum. This dissertation aims to bridge this paucity by performing an advanced three-dimensional outcrop analog investigation and multiscale microporosity studies of these formations. We document the 3D morphology and spatial distribution of the stromatoporoid/coral facies part of the Hanifa reservoir outcrop analog in Wadi Birk, Saudi Arabia, using 3D drone-based digital outcrop model, cores, near-surface geophysical measurements, and deep-learning methodology. We construct a high-fidelity outcrop analog reservoir model from these observations and utilize it for dynamic simulation during waterflood. Further, based on the Upper Jubaila Formation outcrop analog in Wadi Laban, Saudi Arabia, we investigate the influence of microcrystals that host microporosity on petrophysical properties. We upscale the relationships and utilize seismic-derived acoustic-impedance data to arrive at reservoir grid block-scale microporosity distribution. Our results provide a novel and valuable insight into the growth morphology of the stromatoporoid/coral buildups and their relationship with subsurface fluid flow previously unknown for the Hanifa reservoir. The results demonstrate that sweep efficiency is greatly influenced by the interaction between the buildup clusters with the background strata. Our results also provide a practical method to integrate key sub-grid scale micro and macro heterogeneities into reservoir grid block-scale property models.

<p> An assemblage of coral skeletons of the species Desmophyllum cristagalli were obtained from the top of Orphan Knoll, 550 km northeast of Newfoundland, from depths of approximately 1600 and 1800 m. The corals were observed for their macro- and micro-boring assemblages, and the boring morphologies documented, using binocular and scanning electron microscopy. Samples of coral were embedded with resin and etched for examination of the micro-boring assemblages.</p> <p> The largest volumetric amount of skeletal material removed was by sponges forming Entobia. This further corroborates the assumption that various species of boring sponges are distributed ubiquitously throughout a wide bathymetric range.</p> <p> Four distinct fungal forms were found, two tubular forms interpreted to be hyphal filaments and two bulbous forms interpreted to be sporangia. These forms were described on the basis of their shape, size, mode of branching, association with other structures and texture. They were then compared to other micro-boring assemblages found in previous studies from various bathymetric ranges. Some forms described in this study were found to be similar to forms described in other studies. Other forms in this study were not found to be documented. It is suggested, therefore, that certain forms, as well as low ichnodiversity, may indicate deeper water environments.</p> <p> Destructive micritization structures were also found in resin casts as well as in thin section. The extent of micritization may indicate the intensity of the parameters at the substrate that affect carbonate dissolution, such as CaCO3 and CO2 concentrations, pH, temperature, and salinity. It would therefore indicate the ambient water conditions at the substrate. If a sufficiently large database could be obtained, as well as distinct separation of the parameters responsible for carbonate dissolution, micritization may be used in a mapping of the carbonate compensation depth through time and depth ranges.</p> / Thesis / Bachelor of Science (BSc)

No description available.

A geodatabase and a data management program have been created to store and manipulate cave and karst feature data from the Bahamas. A geographic information system was used to recognize any spatial patterns in the cave and karst data from San Salvador Island. Elevation data for banana holes, vadose pits and flank margin caves were obtained from a digital elevation model and are consistent with values predicted by the Carbonate Island Karst Model. The slope and aspect of the hill on which a flank margin cave is found showed no relationship to cave sizes and shapes, emphasizing the hypogenic nature of flank margin caves. The digital elevation model further demonstrated the position of lakes on San Salvador Island during the last interglacial (OIS 5e) highstand, and the lack of flank margin caves along the shores of these lakes provides evidence for a paleoclimate on San Salvador Island similar to today?s.