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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

The hydration, microstructure, and mechanical properties of vaterite calcined clay cement (VC 3 )

Limestone (calcite) calcined clay cement (LC 3 ) is a promising low-CO 2 binder, but the low activity of calcite cannot compensate the reduction in clinker factor, resulting in low one-day strength and limiting its broad applications. As recent carbon capture and utilization technologies allow scalable production of vaterite, a more reactive CaCO 3 polymorph, we overcome the challenge by introducing vaterite calcined clay cement (VC 3 ), inspired by the vaterite-calcite phase change. In the present study, VC 3 exhibits higher compressive strengths and faster hydration than LC 3 . Compared to hydrated LC 3 , hydrated VC 3 exhibits increased amount of hemi- and mono-carboaluminate formation and decreased amount of strätlingite formation. With gypsum adjustment, the 1-day strength of VC 3 is higher than that of pure cement reference. Finally, VC 3 , a low-CO 2 binder, presents great potential as a host of the metastable CaCO 3 for carbon storage and utilization and as an enabler of carbon capture at gigaton scales.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Relative permeabilities for two-phase flow through wellbore cement fractures

Multiple fluids are likely to exist in fractures and flow paths associated with leaky wellbores, including liquids (e.g., crude oil) and gases (e.g., gas exsolved from liquid). These fluids occupy and move through different portions of the pore spaces within the fractures depending on many factors, including fluid properties, fracture size, and the amount of the different fluids. Upward leakage of any phase, through the fracture, can contaminate water-bearing formations, create hazardous surface conditions, and compromise the functionality of the wellbore. Early signs of wellbore leaks may be expressed by anomalous pressure behavior at surface monitoring points on cavern storage wells. These pressure anomalies are difficult to interpret, necessitating knowledge of the factors that affect the multiphase flow in fractures and porous media. These parameters are critical to modeling multiphase flow in fractures. This insight can guide further diagnosis and maximize leak remediation. Here, our study focuses on the relationship of the liquid–gas relative permeabilities for representative variable-aperture wellbore cement fracture. To obtain the relative permeability of each phase, two-phase flow tests were conducted where both fluids were flowing simultaneously through a fractured wellbore cement specimen under a range of factors, namely (1) aperture size, (2) capillary numbers, and (3) viscosity ratio. The flow experiments were conducted under a range of confining stresses and flow velocities, using nitrogen gas and silicone oils (of different viscosities) in a specially designed pressure vessel. The sum of gas and oil relative permeabilities were found to be less than one under all conditions, which indicates that the presence of one phase affects the permeability of the other phase, and vice versa. Since the gas phase flow conditions include a significant inertial flow component in addition to viscous flow, the inertial flow coefficients at different saturation states are presented. The factors affecting the relationship between the relative permeabilities are discussed in detail. A new mathematical model for estimating the relative permeability of wellbore cement fracture is presented and experimentally validated.

58 GEOSCIENCES↗
DOE OSTI2022

Opening-mode fracturing and cementation during hydrocarbon generation in shale: An example from the Barnett Shale, Delaware Basin, West Texas

Relative timing of fracturing is a key input for predictive fracture models, but timing information for fractures is commonly difficult to obtain. In this study, we used crosscutting relations and fluid inclusion assemblage temperatures from fracture cements from a few well-documented sampled fractures, combined with a one-dimensional burial history model, to establish timing for three generations of opening-mode fractures in a Barnett Shale core from the southern part of the Delaware Basin, Pecos County, West Texas. A burial history model is presented for the cored well and matched to measured vitrinite reflectance in samples from the core, and bottomhole temperature in the well. Here, the earliest fractures (group 1) likely formed due to early fluid-expulsion events (ca. 300 Ma) and were folded during host-rock compaction. Later group 2 fractures are sealed with fibrous barite containing primary, liquid hydrocarbon inclusions (mean homogenization temperature [T h ] = –9°C) and aqueous fluid inclusions (mean T h = 108.1°C). Group 2 fractures likely formed in response to fluid overpressure associated with cracking of type II kerogen to oil. Group 3 vertical fractures are up to 2 m in height with kinematic apertures ranging from less than 0.05 to 1.4 mm, partly open, and strike dominantly 010°–020°. Sequentially trapped aqueous fluid inclusions in fracture-spanning quartz cement bridges (mean T h = 110°C in crack-seal texture and 128°C in post-crack-seal fracture cement) record fracture opening under increasing temperature, inferred to reflect increasing burial, with continued overpressuring during the Triassic to Late Cretaceous. Some group 3 fractures may have continued to fill during Cenozoic uplift.

02 PETROLEUM↗
DOE OSTI2022

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↗
DOE OSTI2023

Motion of Air Bubbles in a Cement Slurry

The dynamics of air (gas) bubbles in a column of cement slurry is examined numerically. The air injected at the bottom of a laboratory-scale column through a porous distributor plate spatially distributes and migrates as a swarm of bubbles throughout the slurry toward the freeboard. The two-phase system of the cement slurry and the air bubbles is modeled using the conservation equations of mass and linear momentum in the framework of the volume-of-fluid (VOF) approach. The cement slurry is modeled using the Herschel–Bulkley and Bingham fluid models. Results show that the mean Sauter diameter and the mean rise velocity of the bubbles decrease with the gas flow rate. Meanwhile, it is found that the rising of the bubbles is controlled by breakup events, along with relatively weak path instabilities of the bubbles resulting in relatively straight trajectories, independent of the gas flow rate. The extent of the yielded region appears larger for the Herschel–Bulkley model compared to the Bingham fluid model (by approximately 10%).

36 MATERIALS SCIENCE↗
DOE OSTI2020

A comparative study on the physicochemical characteristics of nanoparticles released in vivo from CoCrMo tapers and cement–stem interfaces of total hip replacements

The good biocompatibility and corrosion resistance of the bulk CoCrMo alloy has resulted in it being used in the manufacture of implants and load bearing medical devices. These devices, however, can release wear and corrosion products which differ from the composition of the bulk CoCrMo alloy. The physicochemical characteristics of the particles and the associated in vivo reactivity are dictated by the wear mechanisms and electrochemical conditions at the sites of material loss. Debris released from CoCrMo hip bearings, taper junctions, or cement–stem interfaces can, therefore, have different chemical and morphological characteristics, which provide them with different in vivo toxicities. Here, we propose to assess and compare the characteristics of the particles released in vivo from CoCrMo tapers and cement–stem interfaces which have received less attention compared to debris originating from the hip bearings. The study uses state–of–art characterization techniques to provide a detailed understanding of the size, morphology, composition, and chemistry of the particles liberated from the wear and corrosion flakes from revised hip replacements, with an enzymatic treatment. The phase analyses identified Cr 2 O 3 nanoparticles released from tapers and cement–stem interfaces, whose composition did not vary with origin or particle morphology. The size distributions showed significantly smaller particles were released from the stems, compared to the particles originating from the corresponding tapers. Furthermore, the investigation demonstrates that the tribocorrosive processes occurring at the taper and stem interfaces both result in Cr 2 O 3 nanoparticle formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Mechanisms dominating thixotropy in limestone calcined clay cement (LC3)

Limestone calcined clay cement (LC3) is a green binder with great practical importance for the cement industry. Growing application has increased the need to understand the mechanisms governing its thixotropy for better control of workability. While formation of C-S-H bridges is understood to dominate the thixotropy of ordinary Portland cement, LC3 paste displayed unique thixotropy properties. In this study, focused beam reflectance measurement, zeta potential, 1H nuclear magnetic resonance relaxometry and micro X-ray computed tomography were used to track the colloidal interaction and hydration extent within LC3 paste. Results showed that flocculation due to the negative surface charge and water affinity of calcined clay appears to be the dominating factor. This leads to a reduction of water available to contribute to fluidity of the paste and, in turn, governing the development of thixotropy over time. In addition, the dilution effect due to high clinker substitution diminishes thixotropy growth with time.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Belite cements and their activation

Belite cements, BCs, containing mainly belite, alite and calcium aluminates, are currently used as low heat cements. These binders produce high amounts of C–S–H gel and have very good durability properties which are reviewed. Additional advantages include: (i) lower limestone demand, with lower associated CO{sub 2} emissions; (ii) lower energy demand; (iii) lower kiln operating temperature, which means lowering CO{sub 2} and NO{sub x} emissions from fuel burning; and (iv) lower temperature increase at early hydration age. However, early-age strength developments are not competitive with those of Portland cements. Hence, to improve their early-age strength developments is a research priority known as activation. This enhancement can be attained by three compatible approaches: (i) chemical, (ii) physical; and (iii) admixture activations. The current research status for BCs activation is reviewed including: cost-effective element substitutions to stabilize high-temperature forms; fast cooling, milling and mild temperature hydration as physical activation; and the use of C–S–H seeds as admixture activation. After discussion of the resulting microstructures, a research outlook is exercised.

36 MATERIALS SCIENCE↗
DOE OSTI2021

A new hypothesis for air loss in cement systems containing fly ash

Although there are many benefits gained from incorporating fly ash into concrete, carbon contamination in the fly ash has been shown to interfere with the efficacy of organic additives in an unpredictable manner. This work uses surface tension measurements to quantify the adsorption of air-entraining agents (AEA) onto cement and fly ash. Both the adsorption capacity of the adsorbents and the adsorption isotherms indicate that the fly ash particles, rather than the carbon itself, dominate adsorption in a carbon-contaminated ash in cement pore solution. We propose that adsorption onto fly ash particles and cement actually improve air entrainment via Pickering stabilization. While the carbon is still expected to contribute to air loss via hydrophobic adsorption of the surfactants, we suggest that the primary way in which the carbon interferes is by shielding surfactant-coated fly ash particles from participating in air development and Pickering stabilization during mixing.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Quantifying the anomalous water absorption behavior of cement mortar in view of its physical sensitivity to water

The one-dimensional water absorption into cement-based materials, possibly the simplest case of unsaturated water flow playing a fundamental role in predicting mass transport and durability, is still far from being completely understood due to several puzzling anomalies. Considering the water sensitivity of C-S-H gels (swell upon wetting and contract upon drying), a modified Richards equation (MRE) is proposed to quantify the anomalous water absorption into cement-based materials of changing porosity. Consistent experimental tests on a cement mortar and calculations indicate that the MRE with time-decaying water permeability can quantitatively capture the long-term absorption with two linear stages and a nonlinear transition stage between them. The water sensitivity is validated to be responsible for the anomalous deviation of water absorption from the classical square root of time law. It also partially contributes to the anomalous dependence of sorptivity on the temperature-dependent surface tension and viscosity of water and many organic liquids.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Mechanistic modeling of CO 2 well leakage in a generic abandoned well through a bridge plug cement-casing gap

Both known and unmapped plugged and abandoned wells are potential leakage pathways for CO 2 from geologic carbon sequestration (GCS) sites. Although many abandoned wells have cement bridge plugs installed to prevent leakage, the seal between the cement and the inner casing wall is subject to failure. In this study, we carried out detailed T2Well simulations of cases of sudden non-Darcy flow of CO 2 and brine leakage up the gap between a cement plug and the inner steel casing wall that becomes a fully connected flow path during the post-injection period. The goal of our study was two-fold: (1) to understand the dynamics, rates, and the characteristic temporal signals associated with the onset of leakage through various gap-aperture sizes, and (2) to suggest potential monitoring strategies based on the findings. Simulation results show that the leakage of CO 2 and brine upward is transient with interesting phase interference behavior. Time-dependent oscillatory flows with varying pressure, temperature, and flow rates of CO 2 and brine show strong dependence on gap aperture. Phase-change and decompression lead to very low temperatures at the top of the well for gap apertures larger than 4 mm suggesting that remote thermal monitoring at the ground surface may be an effective way of monitoring even if well locations are not known a priori. Pressure in the well is also indicative of CO 2 leakage. The temporal patterns of changing temperature and pressure may be useful diagnostic signals for leakage detection. Finally, these transient leakage signals may provide information on the cause of leakage and/or characteristics of the flow path that could inform effective remediation design and execution approaches.

58 GEOSCIENCES↗
DOE OSTI2022

Surface interfacial analysis of simulant high level nuclear waste glass dissolved in synthetic cement solutions

Abstract The corrosion mechanisms and kinetics of a Mg-rich alkali aluminoborosilicate glass simulating UK high-level waste (CaZn28) were investigated upon dissolution in synthetic cement solutions. Dissolution varied as a function the different pH and alkali/alkaline earth content of each cement solution. High resolution microscopy and spectroscopy techniques ascertained the nature of the interface between the glass and the cement solutions. TEM-EDS revealed alkali- and alkaline earth-rich silica gels, into which K, Ca and Mg were incorporated. TEM-SAED, combined with synchrotron micro-focus XRD, identified the ubiquitous precipitation of the Mg-aluminate layered double hydroxide phase, meixnerite (Mg 6 Al 2 (OH) 18 ·4H 2 O), in addition to goethite (FeOOH) and crystalline silica. The C-S-H phase, tobermorite (Ca 5 Si 6 O 16 (OH) 2 ·4H 2 O), was identified in the most Ca-rich solution only. These data give insight to the role of alkali/alkaline earth-rich solutions in the dissolution or radioactive waste glasses, of importance to the final disposition in a geological disposal facility.

Corkhill, Claire L. (ORCID:0000000274883219)↗
DOE OSTI2021

Radioactive decay of $\mathrm {{}^{90}Sr}$ in cement: a non-equilibrium first-principles investigation

Cement is an inexpensive and relatively easily manageable material that is used as a last barrier for nuclear waste disposal. Under these conditions, the cement is in contact with low radiation doses, but there is a distinct possibility of being contaminated with radioactive products. Of particular concern is the medium lived half-life product 90 Sr (28.8 years) due to its ability to replace Ca. 90 Sr undergoes β-decay to 90 Y which, in turn, β-decays to stable 90 Zr. In this work, we discuss systematically the chain of non-equilibrium processes that result as a consequence of β-decay events in cement. We first use density functional-based methods to study the consequences of the sudden increase of the nuclear charge from Z to Z+1, a possible induced ionization and the perturbation of the surrounding electronic charge. Secondly, we use molecular dynamics simulations to study the recoil of the daughter nucleus. Finally, we discuss the damage caused by the ionization cascade produced during the propagation of the β-electron and the resulting chemical and structural perturbation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Hexagonal Boron Nitride Reinforced Multifunctional Well Cement for Extreme Conditions

The overarching objective of this project was to provide a system approach for developing the next generation of well cementing with remarkable multifunctional, high performance characteristics including mechanical, thermal, rheological and durability properties to prevent offshore spill and leakage at extreme high temperature, high pressure (HTHP) and corrosive conditions. Building on our scientifically illustrated principles, the objective of Phase I was to develop and tune our current proof-of-concept hexagonal boron-nitride (hBN)/cement composite to offer the best hybrid nanostructure, and optimum slurry formulation and rheological properties in environments with a variety of extreme conditions including high temperature, high pressure, and high acidity. This phase also focused on testing the actual barrier efficiency and performance of our new cement formulation against gas/liquid leakage at HT, and/or corrosive conditions. The objective of Phase 2 was product validation (meeting API/EPA standards), cost/risk analysis, and scale-up to facilitate integration for primary well cementing with no/minimal modification.

02 PETROLEUM↗
DOE OSTI2024

Cements and a Modeling Tool to Calculate their Viability under Various Exploitation Conditions of HT RTES Systems

Primary cementing is the most important operation performed on a subterranean reservoir. 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.

15 GEOTHERMAL ENERGY↗
DOE OSTI2024

Techno-Economic Analysis of Cement Decarbonization Techniques: Oxygen Enrichment vs. Hydrogen Fuel

The Paris Agreement aims to limit global warming, and one of the most polluting sectors is heavy industry, where cement production is a significant contributor. This work briefly explores some alternatives, recycling, reducing clinker content, waste heat recovery, and carbon capture, discussing their advantages and drawbacks. Then, it examines the economic viability and benefits of increasing oxygen concentration in the primary burning air from 21 to 27 vol.%, which could improve clinker production by 7%, and the production of hydrogen through PEM electrolysis to make up 5% of the fuel thermal fraction, considering both in a cement plant producing 3000 tons of clinker per day. This analysis used reference values from Secil, an international company for cement and building materials, to determine the required scale of the oxygen and hydrogen production, respectively, and calculate the CAPEX of each approach. It is concluded that oxygen enrichment can provide substantial fuel savings for a relatively low cost despite a possible significant increase in NOx emissions. However, hydrogen production at this scale is not currently economically viable.

Domingues, Bruno C.↗
DOE OSTI2024

Role of Hydrogen as Fuel in Decarbonizing US Clinker Manufacturing for Cement Production: Costs and CO2 Emissions Reduction Potentials

As a low-carbon fuel, feedstock, and energy source, hydrogen is expected to play a vital role in the decarbonization of high-temperature process heat during the pyroprocessing steps of clinker production in cement manufacturing. However, to accurately assess its potential for reducing CO2 emissions and the associated costs in clinker production applications, a techno-economic analysis and a study of facility-level CO2 emissions are necessary. Assuming that up to 20% hydrogen can be blended in clinker fuel mix without significant changes in equipment configuration, this study evaluates the potential reduction in CO2 emissions (scopes 1 and 2) and cost implications when replacing current carbon-intensive fuels with hydrogen. Using the direct energy substitution method, we developed an Excel-based model of clinker production, considering different hydrogen–blend scenarios. Hydrogen from steam methane reformer (gray) and renewable-based electrolysis (green) are considered as sources of hydrogen fuel for blend scenarios of 5%–20%. Metrics such as the cost of cement production, facility-level CO2 emissions, and cost of CO2 avoided were computed. Results show that for hydrogen blends (gray or green) between 5% and 20%, the cost of cement increases by 0.6% to 16%, with only a 0.4% to 6% reduction in CO2 emissions. When the cost of CO2 avoided was computed, the extra cost required to reduce CO2 emissions is $229 to $358/ metric ton CO2. In summary, although green hydrogen shows promise as a low-carbon fuel, its adoption for decarbonizing clinker production is currently impeded by costs.

Okeke, Ikenna J.↗
NASA NTRS1979

Late diagenetic indicators of buried oil and gas. 2: Direct detection experiment at Cement and Garza fields, Oklahoma and Texas, using enhanced LANDSAT 1 and 2 images

The author has identified the following significant results. The Cement oil field, Oklahoma, was a test site for an experiment designed to evaluate LANDSAT's capability to detect an alteration zone in surface rocks caused by hydrocarbon microseepage. Loss of iron and impregnation of sandstone by carbonate cements and replacement of gypsum by calcite were the major alteration phenomena at Cement. The bedrock alterations were partially masked by unaltered overlying beds, thick soils, and dense natural and cultivated vegetation. Interpreters, biased by detailed ground truth, were able to map the alteration zone subjectively using a magnified, filtered, and sinusoidally stretched LANDSAT composite image; other interpreters, unbiased by ground truth data, could not duplicate that interpretation.

Donovan, T. J.↗