Thermodynamic Modelling of CaO-Al2O3-SiO2-H2O-Based Cements

Most concrete is produced using calcium (alkali) aluminosilicate hydrate (C-(N-)A-S-H)-based cement. However, the chemistry of this phase in many cement-based materials is still not fully understood. This thesis presents a structural and thermodynamic investigation of C-(N-)A-S-H and C-(N-)A-S-H-based cements to provide insight into the chemistry of these materials. A mixed cross-linked and non-cross-linked tobermorite-like structural model for C-(N)-A-S-H is developed (the CSTM), which more appropriately describes the spectroscopic information available for this phase. Application of the CSTM to a Na2SiO3-activated slag cement cured for 56 and 180 days indicates the presence of a poorly-crystalline zeolite-like phase. The role of Al in cross-linking of C-(N-)A-S-H is also studied, which provides a more advanced description of the chemistry and structure of C-(N-)A-S-H than previously reported. A thermodynamic model for C-(N-)A-S-H (CNASH_ss) is derived, which greatly advances the utility of thermodynamic modelling of C-(N-)A-S-H-based cements by explicitly defining Al and alkali uptake in this phase. The chemistry of alkali-activated slag (AAS)-based cements is simulated using CNASH_ss and an ideal solid solution thermodynamic model for MgAl-OH-LDH that is also developed in the thesis. This analysis provides a good description of Na2SiO3-activated slag cement chemistry and accurately predicts chemical shrinkage in this material. Phase diagrams for NaOH, Na2SiO3, Na2Si2O5 and Na2CO3-activated slag-based cements are also simulated. These results can be used to design the chemistry of AAS-based materials. A detailed analysis of C-(N-)A-S-H solubility is presented, for Ca, Al, Si and alkali concentrations most relevant to C-(N-)A-S-H-based cements and at temperatures of 7-80°C. Solubility products for alkali-free C-(N-)A-S-H change slightly between 7°C and 80°C and as a function of Al/Si ratio. However, less soluble C-(N-)A-S-H is formed at higher Ca and alkali content. These results are important for understanding the stability of C-(N-)A-S-H in the majority of cement-based materials used worldwide

Implications of Emerging Vehicle Technologies on Rare Earth Supply and Demand in the United States

We explore the long-term demand and supply potentials of rare earth elements in alternative energy vehicles (AEVs) in the United States until 2050. Using a stock-flow model, we compare a baseline scenario with scenarios that incorporate an exemplary technological innovation: a novel aluminum–cerium–magnesium alloy. We find that the introduction of the novel alloy demonstrates that even low penetration rates can exceed domestic cerium production capacity, illustrating possible consequences of technological innovations to material supply and demand. End-of-life vehicles can, however, overtake domestic mining as a source of materials, calling for proper technologies and policies to utilize this emerging source. The long-term importing of critical materials in manufactured and semi-manufactured products shifts the location of material stocks and hence future secondary supply of high-value materials, culminating in a double benefit to the importing country. This modeling approach is adaptable to the study of varied scenarios and materials, linking technologies with supply and demand dynamics in order to understand their potential economic and environmental consequence

YSTAFDB, a unified database of material stocks and flows for sustainability science

We present the Yale Stocks and Flows Database (YSTAFDB), which comprises most of the material stocks and flows (STAF) data generated at the Center for Industrial Ecology at Yale University since the early 2000s. These data describe material cycles, criticality, and recycling in terms of 62 elements and various engineering materials, e.g., steel, on spatial scales and timeframes ranging from cities to global and the 1800s to ca. 2013. YSTAFDB integrates this diverse collection of STAF data, previously scattered across various non-uniformly formatted electronic files, into a single data structure and file format. Here, we discuss this data structure as well as the usage and formatting of data records in YSTAFDB. YSTAFDB contains 100,000+ data records that are all situated in their systems contexts, with additional metadata included as available. YSTAFDB offers a comprehensive basis upon which STAF data can be accumulated, integrated, and exchanged, and thereby improves their accessibility. Therefore, YSTAFDB facilitates deeper understanding of sustainable materials use and management, which are key goals of contemporary sustainability science

Effect of Gypsum on the Early Hydration of Cubic and Na-Doped Orthorhombic Tricalcium Aluminate

The tricalcium aluminate (C3A) and sulfate content in cement influence the hydration chemistry, setting time and rheology of cement paste, mortar and concrete. Here, in situ experiments are performed to better understand the effect of gypsum on the early hydration of cubic (cub-)C3A and Na-doped orthorhombic (orth-)C3A. The isothermal calorimetry data show that the solid-phase assemblage produced by the hydration of C3A is greatly modified as a function of its crystal structure type and gypsum content, the latter of which induces non-linear changes in the heat release rate. These data are consistent with the in situ X-ray diffraction results, which show that a higher gypsum content accelerates the consumption of orth-C3A and the subsequent precipitation of ettringite, which is contrary to the cub-C3A system where gypsum retarded the hydration rate. These in situ results provide new insight into the relationship between the chemistry and early-age properties of cub- and orth-C3A hydration and corroborate the reported ex situ findings of these systems

Effect of gypsum on the early hydration of cubic and Na-doped orthorhombic tricalcium aluminate

The tricalcium aluminate (C3A) and sulfate content in cement influence the hydration chemistry, setting time and rheology of cement paste, mortar and concrete. Here, in situ experiments are performed to better understand the effect of gypsum on the early hydration of cubic (cub-)C3A and Na-doped orthorhombic (orth-)C3A. The isothermal calorimetry data show that the solid-phase assemblage produced by the hydration of C3A is greatly modified as a function of its crystal structure type and gypsum content, the latter of which induces non-linear changes in the heat release rate. These data are consistent with the in situ X-ray diffraction results, which show that a higher gypsum content accelerates the consumption of orth-C3A and the subsequent precipitation of ettringite, which is contrary to the cub-C3A system where gypsum retarded the hydration rate. These in situ results provide new insight into the relationship between the chemistry and early-age properties of cub- and orth-C3A hydration and corroborate the reported ex situ findings of these systems

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C₃A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C₃A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C₃A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C₃A, reducing its zeta potential to negative values at pH >12. The S and Ca <i>K</i>-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO₄^2– on the partially dissolved C₃A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C₃A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca–S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C₃A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C₃A and thus PC systems, which is important to better controlling the workability of fresh PC concrete

The SDSS-III Baryon Oscillation Spectroscopic Survey: Quasar Target Selection for Data Release Nine

The SDSS-III Baryon Oscillation Spectroscopic Survey (BOSS), a five-year spectroscopic survey of 10,000 deg^2, achieved first light in late 2009. One of the key goals of BOSS is to measure the signature of baryon acoustic oscillations in the distribution of Ly-alpha absorption from the spectra of a sample of ~150,000 z>2.2 quasars. Along with measuring the angular diameter distance at z\approx2.5, BOSS will provide the first direct measurement of the expansion rate of the Universe at z > 2. One of the biggest challenges in achieving this goal is an efficient target selection algorithm for quasars over 2.2 < z < 3.5, where their colors overlap those of stars. During the first year of the BOSS survey, quasar target selection methods were developed and tested to meet the requirement of delivering at least 15 quasars deg^-2 in this redshift range, out of 40 targets deg^-2. To achieve these surface densities, the magnitude limit of the quasar targets was set at g <= 22.0 or r<=21.85. While detection of the BAO signature in the Ly-alpha absorption in quasar spectra does not require a uniform target selection, many other astrophysical studies do. We therefore defined a uniformly-selected subsample of 20 targets deg^-2, for which the selection efficiency is just over 50%. This "CORE" subsample will be fixed for Years Two through Five of the survey. In this paper we describe the evolution and implementation of the BOSS quasar target selection algorithms during the first two years of BOSS operations. We analyze the spectra obtained during the first year. 11,263 new z>2.2 quasars were spectroscopically confirmed by BOSS. Our current algorithms select an average of 15 z > 2.2 quasars deg^-2 from 40 targets deg^-2 using single-epoch SDSS imaging. Multi-epoch optical data and data at other wavelengths can further improve the efficiency and completeness of BOSS quasar target selection. [Abridged]Comment: 33 pages, 26 figures, 12 tables and a whole bunch of quasars. Submitted to Ap