Kinoite, a new hydrous copper calcium silicate mineral from Arizona
Hydrous Cu-Ca silicate mineral /kinoite/ from Arizona occurring as single crystals and veinlets
Anthony, J. W.↗
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Precipitation of calcium–alumino–silicate–hydrate gels: The role of the internal stress
Concrete gains its strength from the precipitation of a calcium–alumino–silicate–hydrate (C–A–S–H) colloidal gel, which acts as its binding phase. However, despite concrete’s ubiquity in the building environment, the atomic-scale mechanism of C–A–S–H precipitation is still unclear. Here, we use reactive molecular dynamics simulations to model the early-age precipitation of a C–A–S–H gel. We find that, upon gelation, silicate and aluminate precursors condensate and polymerize to form an aluminosilicate gel network. Notably, we demonstrate that the gelation reaction is driven by the existence of a mismatch of atomic-level internal stress between Si and Al polytopes, which are initially experiencing some local tension and compression, respectively. The polymerization of Si and Al polytopes enables the release of these competitive stresses.
Zhao, Cheng↗
Advanced ceramic coating development for industrial/utility gas turbines
A program was conducted with the objective of developing advanced thermal barrier coating (TBC) systems. Coating application was by plasma spray. Duplex, triplex and graded coatings were tested. Coating systems incorporated both NiCrAly and CoCrAly bond coats. Four ceramic overlays were tested: ZrO2.82O3; CaO.TiO2; 2CaO.SiO2; and MgO.Al2O3. The best overall results were obtained with a CaO.TiO2 coating applied to a NiCrAly bond coat. This coating was less sensitive than the ZrO2.8Y2O3 coating to process variables and part geometry. Testing with fuels contaminated with compounds containing sulfur, phosphorus and alkali metals showed the zirconia coatings were destabilized. The calcium titanate coatings were not affected by these contaminants. However, when fuels were used containing 50 ppm of vanadium and 150 ppm of magnesium, heavy deposits were formed on the test specimens and combustor components that required frequent cleaning of the test rig. During the program Mars engine first-stage turbine blades were coated and installed for an engine cyclic endurance run with the zirconia, calcium titanate, and calcium silicate coatings. Heavy spalling developed with the calcium silicate system. The zirconia and calcium titanate systems survived the full test duration. It was concluded that these two TBC's showed potential for application in gas turbines.
Vogan, J. W.↗
Uptake of aqueous heavy metal ions (Co2+, Cu2+ and Zn2+) by calcium-aluminium-silicate-hydrate gels
Highlights: • C-A-S-H gels containing metal ions (Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated by a sol-gel technique. • Uptake mechanism and immobilization capacity of divalent metal ions by C-A-S-H are elucidated. • Up to ~55–60 mol% of Zn can be incorporated in defective tobermorite-type C-A-S-H. • Metal uptake by C-A-S-H is controlled mainly by isomorphous substitution for Ca ions. • Crystal-chemical features of C-A-S-H gels and implications for practical application are discussed. Calcium-aluminium-silicate-hydrate (C-A-S-H) gels containing heavy metal ions (Me: Co{sup 2+}, Cu{sup 2+} or Zn{sup 2+}) were precipitated at different Me/Si molar ratios to study the uptake mechanism and immobilization capacity. Aqueous solution chemistry and solid-phase characterization using XRD, FTIR, ESEM-EDX, TEM-HAADF and TG-DSC methods reveal threshold values for ion substitution of ~55–60 mol% for Zn, ~30–40 mol% for Co and ~25–30 mol% for Cu in defective tobermorite-type C-A-S-H with (Ca + Me)/(Si + Al) molar ratios from 0.86 to 1.04. At higher aqueous Me concentrations, Me (chloride) hydroxides start to co-precipitate. The uptake mechanism of Me ions by C-A-S-H is based on (i) isomorphous substitution of Me for Ca in the CaO layer, (ii) ion exchange in the interlayer, (iii) tetrahedral substitution (Zn) within the dreierketten chains and (iv) surface adsorption onto the C-A-S-H gel structure. Systematics in crystal-chemistry of Me-bearing C-A-S-H and implications for application and performance in natural and man-made settings are discussed.
36 MATERIALS SCIENCE↗
Near-field infrared microscopy: A novel analytic mapping technique to nanocharacterize calcium silicate-based cement materials
Infrared imaging via scattering-type scanning near-field optical microscopy (s-SNOM) allows chemical mapping of organic and inorganic materials with nanoscale spatial resolution. However, its potential adaptation to the complex multiphase structure of Portland cement is yet to be explored. Here we demonstrate the successful implementation of s-SNOM to spatially resolve coexisting chemical phases in tricalcium silicate, Portland cement's main compound, with 20-nm resolution. We found that s-SNOM is sensitive to different anhydrous polymorphic phases, revealing nanoscale domains that are ‘invisible’ to other microscopic techniques. Furthermore, s-SNOM's ability to distinguish the unhydrated and hydrated phases signifies its great promise as an analytical tool to study the complex hydration process of cement. The key to s-SNOM's application was nano-modifying the surface roughness of the cement samples, allowing nanoscale infrared imaging without topographical artifacts. Our study opens a window for infrared spectral microscopy in cement and other porous inorganic materials.
36 MATERIALS SCIENCE↗
TCF - Sustainable Well Cement for Geothermal, Thermal Recovery, and Carbon Storage wells
Primary cementing is the most important operation performed on a subterranean well. Cement, placed in the annulus between the casing and the formations, serves as a hydraulic seal preventing fluids and gas migrations, protecting steel casing from corrosion, and supporting the well structure. Poor cementing jobs can be directly responsible for wells not reaching their full capacity, casing corrosion, compromised well integrity and, in the worst-case scenarios, well collapse. Geothermal, thermal recovery, and carbon storage wells offer environments that are especially difficult for cements to survive while the required lifespan of these wells can be years. In these wells currently used cements cannot provide durable well integrity, and new solutions are necessary. The necessity of stabilizing the electric grid, increasing its flexibility, and providing energy on demand will further expand the market of durable cement solutions for applications in high-temperature underground reservoir thermal energy storage wells (HT RTES). The design challenges of special cement systems for such wells originate from chemistry limitations of currently used well cements, aggressive environments, temperature and repeated shock conditions associated with them, and very weak formations that are not uncommon in these wells. During the last 70 years the most common systems for thermal-well construction have been Ordinary Portland Cement (OPC) (absolute majority of the wells), silica-lime system, and high aluminum cement-containing formulations. The major issues of calcium-silicate hydrates, that form during the hydration of OPC resulting in hardened material, are their poor chemical resistance to acids due to the calcium interactions with acid anions followed by its eventual dissolution, even in mild acids, such as carbonic acid from CO 2 dissolution, and inadequate bonding to the steel causing serious casing corrosion problems (Sugama & Pyatina, 2019). Performance of OPC-based cement may be significantly improved with organic additives; however, those are limited by their temperature stability. An alternative to calcium-silicate cement was developed by BNL and commercialized by Halliburton as ThermaLock TM cement. Calcium-aluminate-phosphate-based chemistry of the material allowed overcoming acid-resistance problems of OPC, especially in CO 2 -rich geothermal environments. In 2012-2015, building upon this experience, BNL developed Thermal Shock Resistant Cement (TSRC) with the support of Geothermal Technology Office (GTO) of DOE. TSRC has high-temperature stable chemistry, superior properties of cement-metal casing bond and corrosion protection (4-times better than currently used OPC-based formulation), significantly outperforms common well-cements in thermal-shock tests, has self-healing properties, and like ThermaLock TM is CO 2 resistant incorporating carbonate ions into stable hydrates (Gill et al., 2012).
15 GEOTHERMAL ENERGY↗
Microbial Curing of Cement for Energy Applications
Rutgers University, Lawrence Livermore National Laboratory, and the University of Arizona executed this program over 36 months with a 4-Task Program: (M1)-Microbial Engineering (M2)-Microstructure Modelling, (M3) Cement and Concrete Formulation, (M4)-Techno-economic analysis (TEA) and lifecycle assessment (LCA). This program developed a new carbonate cement concrete manufacturing process called microbial curing (MBC). MBC utilizes in-situ microbial production of CO 2 that dissolves into pore-bound water to carbonate a cementitious material creating a bonding matrix of CaCO 3 and SiO 2 that hardens and densifies the material. This is the first work of this type where calcium silicate was used in microbial studies. All other work reported in the literature always used a soluble form of calcium. This final report describes the work done in the final quarter, the best procedures and results, and the final techno-economic and lifecycle analyses. This quarter, we cast and cured twenty-five (4”x8”) cylinder samples. The compressive strength, split tensile, Young’s modulus, chloride permeability, and creep measurements were performed. These measurements demonstrated that MBC of calcium silicate concrete exhibits scaling problems due to the escape of ammonia gas, a product of the microbial reaction to generate CO 2 . As curing proceeds, the ability for the gas to escape from within the cylinder is restricted by the outer cylindrical portions densifying, making the outer portion highly impermeable to gas flow. In contrast, the small samples cured are uniformly cured, forming materials whose mechanical properties are 7x better than the large samples. This problem needs to be solved before this technology can be commercialized. The techno-economic and lifecycle analyses indicate that the technology developed in this program exhibits a significant opportunity to reduce the cost of cement and CO 2 emissions associated with concrete, provided the curing issue associated with larger samples can be addressed.
36 MATERIALS SCIENCE↗
Scalable electrified cementitious materials production and recycling
The production of Portland cement, the industry-standard cement, contributes ~8% of global CO 2 emissions through fossil-fuel heating and decomposition of limestone (the primary cement raw material). Decarbonization, e.g., via direct electrification, of this 200-year-old liming routine is extremely challenging at the industry scale. We propose a scalable electrochemical decarbonization approach to circumvent the limestone use by switching to carbon-free calcium silicates from abundant minerals and recycled concrete. Water electrolysis produces protons and hydroxides to drive a pH gradient that accelerates Ca 2+ ion leaching from calcium silicates and captures atmospheric CO 2 to form carbon-negative CaCO 3 , which serves as the feedstock for cement manufacturing or as the carbon-mineralized product for cement substitution with permanent carbon storage. Value-added co-products amorphous silica and green H 2 further enhance cement performance and supplant fossil fuels for net-zero transition, respectively. The products readily meet present-day regulatory standards and demands, and the approach readily synergizes with business-as-usual cement manufacturing and concrete construction, which are important for upscaling and structural safety, promising ready reception by the public and industries. Blended Portland cement produced through our approach with carbon-negative CaCO 3 and silica demonstrates enhanced resilience and achieves carbon neutrality or negativity when incorporating storage or circulation of CO 2 from cement plant flue gas, respectively. This low-cost, electrochemical cement production approach using abundant ubiquitous raw materials enables electrification, transition to clean fuel, and decarbonization at a gigaton scale.
36 MATERIALS SCIENCE↗
Thermal barrier coatings for thermal insulation and corrosion resistance in industrial gas turbine engines
Four thermal barrier coatings were subjected to a 500-hour gas turbine engine test. The coatings were two yttria stabilized zirconias, calcium ortho silicate and calcium meta titanate. The calcium silicate coating exhibited significant spalling. Yttria stabilized zirconia and calcium titanate coatings showed little degradation except in blade leading edge areas. Post-test examination showed variations in the coating due to manual application techniques. Improved process control is required if engineering quality coatings are to be developed. The results indicate that some leading edge loss of the coating can be expected near the tip.
Vogan, J. W.↗
New interaction potentials for alkaline earth silicate and borate glasses
New interaction potentials were developed for molecular dynamics simulations to study the role of Mg and Ca in modifying the structure and properties of alkaline earth silicates and borates. Competition between the depolymerization of the silica network and the formation of new bonds between oxygen atoms and modifiers leads to the enhancement of the elastic moduli with increasing modifier content in alkaline earth silicate glasses. Compared with calcium silicate, the higher elastic moduli of magnesium silicate result from a higher connectivity of the overall glass network due to the incorporation of fourfold coordinated magnesium and a more rigid connection between oxygen atoms and modifiers. In contrast to the silicates, the effect of modifier on the elastic moduli of alkaline earth borates is dominated by the formation of fourfold coordinated boron (N 4 ). Calcium borate with higher N 4 shows a more rigid network structure and higher elastic moduli.
36 MATERIALS SCIENCE↗
Predicting zeolites’ stability during the corrosion of nuclear waste immobilization glasses: Comparison with glass corrosion experiments
During the long-term corrosion of nuclear waste glasses under nuclear waste disposal conditions, the precipitation of zeolitic phases has been linked to a delayed acceleration in glass corrosion (known as “Stage III”). Hence, predicting the thermodynamic propensity for zeolites to form upon the dissolution of nuclear waste glasses is key to ensure their long-term performance. Here, we compile a unified, internally-consistent thermodynamic database “clay20” to estimate the stability of clay and feldspar phases relevant to nuclear waste immobilization glasses, including beidellite(Mg, Ca, Na, K), kaolinite, montmorillonite(Mg, Ca, Na, K), nontronite(Mg, Ca, Na, K), saponite(Ca, Na, K), and albite. Based on this, we report a geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. We show that this approach offers a realistic description of the stability of the secondary phases forming during the dissolution of two archetypical model nuclear glasses (namely, the International Simple Glass, ISG, and WVUTh-203) under conditions relevant to nuclear waste disposal (T = 90°C, p = 1 bar) as a function of pH. We find that the formation of silica and clay secondary phases is thermodynamically favored at low pH (pH < 10), whereas, in contrast, zeolite (analcime) and calcium–silicate–hydrate phases are favored at high pH (pH > 10.5). This suggests that thermodynamics (i.e., not solely kinetics) plays a key role in determining the range of solution pH wherein stage III corrosion may occur, i.e., when zeolite formation is favored.
Zhen-Wu, Bi Yun↗
Pyroxferroite, a new calcium-bearing iron silicate from Tranquillity Base
Calcium-bearing iron silicate /pyroxferroite/ from Apollo 11 lunar Tranquility Base samples, discussing petrographic environment, physical and optical properties
Anderson, A. T.↗
Corrosion resistant thermal barrier coating
A thermal barrier coating system for protecting metal surfaces at high temperature in normally corrosive environments is described. The thermal barrier coating system includes a metal alloy bond coating, the alloy containing nickel, cobalt, iron, or a combination of these metals. The system further includes a corrosion resistant thermal barrier oxide coating containing at least one alkaline earth silicate. The preferred oxides are calcium silicate, barium silicate, magnesium silicate, or combinations of these silicates.
Levine, S. R.↗
Time-dependent water vapor desorption isotherm model of hardened cement paste
Highlights: • Short-term and long-term desorption isotherms of hardened cement paste are reviewed. • Water content at RH depends on both thermodynamic and microstructural equilibria. • An extended GAB equation is proposed to fit the cavitation drop during desorption. • A dynamic time-dependent sorption isotherm model is shown and used for simulations. • Numerical results capture anomalous drying in the same RH as seen experimentally. This study aims to enhance moisture transport modeling by elucidating the so-called anomalous water diffusion in cementitious materials. Water desorption isotherms are measured from samples at various drying stages using techniques with different durations to quantify the impact of the drying duration on the water sorption ability. A single water sorption isotherm does not solely give a relationship between the water content and relative humidity but also represents the state of microstructure. The continuous evolution of a desorption isotherm due to drying-induced microstructural rearrangement is demonstrated. For numerical modeling, the microstructural alteration can be explicitly considered through a dynamic desorption isotherm model, which governs the local thermodynamic equilibrium at the capillary meniscus. This approach is implemented into a multiphase transport code, whose ability to predict drying is validated using literature data. Finally, the effect of prolonged drying on the colloidal nature of the calcium-silicate-hydrate gel is discussed.
36 MATERIALS SCIENCE↗
Chemical degradation of fly ash blended concrete with the seasonal variation of rainwater in a radioactive waste repository: A thermodynamic modeling approach
Highlights: • The thermodynamic model for the cementitious system was successfully developed. • The chemical degradation of concrete was greatly affected by rainwater types. • Inorganic carbon species in rainwater reduced the chemical resistance of concrete. • The durability of concrete to rainwater decreased with increasing fly ash content. This study presents a long-term degradation behavior of fly ash blended concrete in a vault type low- and intermediate-level radioactive waste (LILW) repository by thermodynamic equilibrium calculations using PHREEQC combined with CEMDATA18 database. Since rainwater plays a predominant role as leachate for the concrete waste container in the repository, the effect of chemical properties of seasonal rainwater on the chemical degradation of concrete was analyzed. In addition, the impact of the blending with fly ash on the chemical degradation was evaluated through a gradual replacement of ordinary Portland cement (OPC) by fly ash. Regardless of the replacement level, autumn rainwater showed the greatest influence on the concrete degradation owing to the presence of inorganic carbon species, which induce the carbonation. The resistance of concrete to chemical degradation by rainwater was persistently reduced due to the decreasing formation of portlandite and calcium silicate hydrate (C-S-H) with increasing replacement level.
36 MATERIALS SCIENCE↗
Development of a kinetic-thermodynamic model for lime-stabilization of Na-bentonite
This study presents the first kinetic model to predict the solid and pore solution composition of Na-bentonite clay reacting with slaked lime over a period of 720 days. The model successfully accounts for most experimental data using a single kinetic rate constant. The following sequence of reactions was predicted by the model: initial rapid dissolution of portlandite within the first 7 days, leading to a decrease in pH and dissolved calcium, and concurrent formation of calcium silicate hydrates (C-S-H: jennite), calcium aluminate hydrate (C-A-H: C₄AH₁₃), calcium aluminosilicate hydrates (stratlingite) and hydrotalcite. After 7 days, jennite and stratlingite are predicted to transform into tobermorite-II, contributing to strength development up to 28 days. From 28 to 90 days, continued montmorillonite dissolution is predicted, along with minor formation of ettringite, partial tobermorite-II dissolution, and precipitation of secondary phases such as albite and talc. Experimentally, portlandite dissolution was confirmed by TGA and XRD and found to be complete within 7 days, in agreement with model predictions. However, other predicted solid-phase transformations (e.g., tobermorite-II formation and dissolution, ettringite, albite, and talc formation) could not be conclusively verified through experimental techniques. Aqueous phase measurements confirmed that the pH and Ca trends in solution, and that equilibrium was reached by 90 days.
Chemical kinetics↗
Reaction kinetics during early hydration of calcined phyllosilicates in clinker-free model systems
Investigations of nearly pure, calcined phyllosilicates (“meta-phyllosilicates”) in clinker-free model systems were performed in presence and absence of sulfate. Calorimetric investigations show a pronounced reaction during the early reaction period only for metakaolin. Quantitative in situ X-ray diffraction reveals calcium silicate hydrate formation in the systems with metakaolin and metaillite, but not in those with metamuscovite. Ettringite crystallizes in all systems containing sulfate, where only the metakaolin system reaches the maximum ettringite content possible. The amount of aluminum ions released from 2:1 meta-phyllosilicates seems to be insufficient to reach the maximum content. Differences in portlandite dissolution and bound water indicate adsorption effects of calcium or calcium – sulfate ion pair complexes on surfaces of the calcined clay particles. Thus, the chemical as well as the physical influence of the meta-phyllosilicates must be considered to predict the reaction kinetics of calcined clays during early hydration.
36 MATERIALS SCIENCE↗
Cs retention and diffusion in C-S-H at different Ca/Si ratio
Cement and concrete are commonly used in the construction of repository sites for radioactive wastes. The correct isolation of those contaminants requires good adsorption and low diffusion rates. Both parameters are highly affected by many factors, such as pH, temperature or composition. The large variability of experimental conditions and formulations makes it extraordinarily difficult to tackle the influence of each of them independently in experimental samples. To this effect, molecular dynamics simulations have been employed in this study to investigate the role of the composition in the capacity to retain Cs and diffusivity of these ions in calcium silicate hydrate (C-S-H) gel pores. The results indicate that the adsorption of Cs ions is worsened at high Ca/Si ratios due to a lower interaction of the cations with the C-S-H surface, while hydrophilicity of the C-S-H nanopore rises, resulting in higher long-range ordering and lower diffusion coefficients of Cs ions.
36 MATERIALS SCIENCE↗