The thermodynamic properties of chloride, nitrate and nitrite AFm hydrates have been determined. Investigations of solid solutions and thermodynamic calculations on the influence of these anions on mineralogical changes in cement paste were performed and compared with experiments. To calculate volume changes, densities of principal crystalline phases occurring in cement were critically assessed and tabulated, in some cases with addition of new data. Database was obtained by calculating densities from crystallographic data and unit cell contents. In hydrated cements, anion sites in AFm phase are potentially occupied by OH, SO₄ and CO₃ ions. C1, NO₃ or NO₂ ions readily displace hydroxide, sulfate and carbonate in the AFm structures. Nitrates and nitrites do not have ability to displace chloride from the Friedel’s salt (C1-AFm) though. The binding power of AFm for nitrite/nitrate/chloride was calculated and confirmed experimentally at 25°C. It was observed that presence of chloride, nitrate or nitrite alters the AFm/Aft balance and thereby affect the specific volume of paste solids. It was found that the success of nitrite as a corrosion inhibitor for protection of embedded steel arises from its “smart” behaviour. AFm normally stores and sequesters nitrite. If chloride ingress occurs in service, the AFm undergoes ion exchange, gaining chloride and forming Friedel’s salt, while releasing soluble nitrite ions to the pore fluid. As a result, the aqueous ratio of [NO₂^-]/[C1^-] increases and remains within the passivation range for steel.

Thesis (Professional Degree)--University of Missouri, School of Mines and Metallurgy, 1929. / The entire thesis text is included in file. Typescript. Title from title screen of thesis/dissertation PDF file (viewed November 30, 2009)

Thesis (Ph. D.)--University of Texas at Austin, 2000. / Vita. Includes bibliographical references (leaves 506-525). Available also in a digital version from Dissertation Abstracts.

Thesis--Ph. D., University of Hong Kong. / Offset from typescript.

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The City of Saskatoon is responsible for maintaining approximately 1,100 km of roads including locals, collectors, arterials, and freeways. With the aged state of the road infrastructure, increasing budget constraints limit the City’s ability to maintain existing road infrastructure to an acceptable level of service and to construct new road infrastructure. The infrastructure demands related to urban growth within the City of Saskatoon have caused a shrinking aggregate supply and increasing aggregate demand. In turn, growing demand and dwindling resources for aggregate are resulting in rapid increases to road construction costs. Aggregate sources are a non-renewable resource in Saskatchewan. Therefore, road designers do not have an endless supply of quality aggregates. With limitations of the road building industry and the foreseeable economic growth projected for the City of Saskatoon, it is reasonable to expect that the unit costs of providing conventional pavement structures will continue to increase in Saskatoon. Presently, the primary conventional road building materials include well graded granular base material, subbase, crushed rock and a wearing surface of either conventional hot mix asphalt concrete (HMAC) or Portland cement concrete (PCC). To ensure long term pavement performance, quality aggregate sources are needed in all road design structural layers. Recent years have seen an increased need for substructure drainage systems, therefore increasing the need for high quality crushed rock. City of Saskatoon, like other urban centers, generates significant stock piles of concrete rubble annually. The primary objective of this research was to compare PCC material properties to those of conventional granular materials under realistic field state conditions. The second objective of this research was to validate the economic feasibility of using recycled PCC material within City of Saskatoon road structure through test section design and field test sections’ structural performance. Conventional and mechanistic material characterization was completed for recycled PCC well graded base course and recycled PCC drainage rock derived from PCC rubble, as well as conventional City granular base and drainage rock aggregates from typical City of Saskatoon stockpiles. Conventional testing completed on the samples included physical properties as required by COS aggregate specifications. Micro-Deval testing was also completed to compare the mechanical breakdown of the aggregates tested. Based on the results of the conventional tests performed, the recycled PCC well graded base and the recycled PCC drainage rock were found to meet COS base and drainage rock specifications, respectively. The recycled PCC well graded base material, recycled PCC drainage rock, COS granular base, and recycled PCC well graded base stabilized with different percentages of cement and slow setting type one (SS-1) asphalt emulsion were the research materials mechanistically tested. These materials were mechanistically tested using triaxial frequency sweep characterization to derive the mechanistic material constitutive relations across all the materials. Five repeat samples were gyratory compacted and tested at room temperature using the rapid triaxial testing. To characterize climatic durability, all the samples were moist cured for 28 days, characterized using the rapid triaxial test; then vacuum saturated and then characterized again using the rapid triaxial test. The mechanistic properties measured for the PCC material showed better climatic durability compared to those measured for the virgin aggregates, particularly after climatic durability testing. Prior to vacuum saturation, the conventional COS granular base had a peak dynamic modulus of 457 MPa. Under the same testing conditions, recycled PCC well graded base unstabilized had a stiffness of 1081 MPa; the stabilized PCC samples with two percent cement had a dynamic modulus of 1542 MPa. The radial micro strain and Poisson’s ratio were reduced for well graded PCC materials both unstabilized and stabilized compared to the conventional COS granular base. The conventional granular base had a peak radial micro strain of 194 compared to the untreated recycled PCC well graded base peak radial micro strain of 54 at the same testing parameters of low stress state at a testing frequency of 10 Hz prior to vacuum saturation. The conventional COS granular base samples failed under high deviatoric stress state at a 0.5 Hz testing frequency prior to vacuum saturation, whereas the PCC materials survived all testing frequencies and stress states. However, after vacuum saturation, the unstabilized recycled PCC well graded base samples failed under high stress state under a 10 Hz testing frequency. To validate field structural performance, two road structures within the City of Saskatoon were used as test sections in which recycled PCC drainage rock was used as a structural drainage layer. The first test section was constructed in the east bound lane of Marquis Drive, and the second was completed at the University of Saskatchewan. Prior to construction of both the Marquis Drive and North Road test sections, both sections were tested for peak surface deflections using the heavy weight deflectometer. Segment 1 of Marquis Drive had an average pre construction surface deflection of 1.85 mm under a primary weight limit. Section 1 of North Road had an average pre construction surface deflection of 1.17 mm under primary weight limit. After construction was complete on both test sections using recycled materials including a PCC drainage layer, HWD testing showed post construction peak deflections were significantly lower than the deflections measured pre construction. Recycled PCC well graded base material performed well in mechanistic laboratory analysis. However, the material was not field tested in this research. Mechanistic laboratory and field analysis indicated that recycled PCC drainage rock aggregates met structural performance requirements. The capital cost analysis showed that using recycled PCC drainage rock can reduce the overall cost of road rehabilitation projects when compared to using conventional virgin aggregates, particularly crushed drainage rock. The Marquis Drive section had a cost savings of $89,000, and the University of Saskatchewan section had a cost savings of $75,800 when recycled materials were used in lieu of virgin aggregates to rehabilitate the pavement structure. In addition, no PCC was disposed of in the landfill, saving the City of Saskatoon tipping fees and extending the life of the landfill. This research showed that the crushed PCC rubble is both technically and economically feasible to use as high quality aggregates in City of Saskatoon streets. Based on the findings of this research, the City of Saskatoon should pursue the use of recycled PCC rubble aggregates in urban road construction.

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Current research interest in multi-scale modeling of cement paste requires accurate characterization of the time-dependent mechanical properties of the material, particularly the C-S-H phase. Nanoindentation is evaluated as a tool for measuring both the instantaneous and the short-term viscoelastic properties of cement paste. Atomic force microscopy (AFM) based indentation is compared to conventional nanoindentaion in measuring mechanical properties of cement pastes. Time-dependent solutions are derived to characterize creep indentation tests performed on hardened cement paste and to extract the time-dependent properties. The effect of approximating C-S-H viscoelastic properties with a time-independent Poisson's ratio is discussed, and arguments for utilizing a time-independent Poisson's ratio for short-term response are presented. In evaluating AFM as a mechanical characterization tool, various analytical and numerical modeling approaches are compared. The disparities between the numerical self-consistent approach and analytical solutions are determined and reported. The measured elastic Young's modulus values acquired by AFM indentation tests are compared to Young's modulus values from nanoindentation measurements from cement paste. These results show that the calcium silicate hydrate (C-S-H) phase of hydrated portland cement has different properties on the nanometric scale than on the micron scale. Packing density of C-S-H particles is proposed as an explanation for the disparity in the measured results. The AFM measured uniaxial viscoelastic compliance values are compared to similar values obtained with traditional nanoindentation for the same material. The comparison of these results shows that the calcium silicate hydrate (C-S-H) phase of portland cement has similar but distinct properties on the sub micron scale than on the micron scale. Additionally, the effect of moisture is evaluated by controlling the relative humidity (RH) of the testing environment between 40% and 100% plus, or wet. The viscoelastic compliance appears to be highest at 40% RH and the material appears to be less compliant at higher relative humidity levels. Possible mechanisms controlling the viscoelastic deformation are presented and evaluated in conjunction with the moisture related poromechanical effect.