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At least 883 records · Page 49

Discrete element modeling of indentation tests to investigate mechanisms of CO 2 -related chemomechanical rock alteration

During CO 2 injection into geological formations, petrophysical and geomechanical properties of host formations can be altered due to mineral dissolution and precipitation. Field and laboratory results have shown that sandstone and siltstone can be altered by CO 2 -water mixtures, but few quantitative studies have been performed to fully investigate underlying mechanisms. Based on the hypothesis that CO 2 -water mixtures alter the integrity of rock structure by attacking cements rather than grains, we attempt to explain the degradation of cementation due to long-term contact with CO 2 and water and mechanisms for changes in rock mechanical properties. Many sandstones, including calcite-cemented quartzitic sandstone, chlorite-cemented quartzitic sandstone, and hematite-cemented quartzitic sandstone, contain interparticle cements that are more readily affected by CO 2 -water mixtures than grains. A model that couples the discrete element method and the bonded-particle model is used to perform simulations of indentation tests on synthetic rocks with crystal and random packings. The model is verified against the analytical cavity expansion model and validated against laboratory indentation tests on Entrada sandstone with and without CO 2 alteration. Sensitivity analysis is performed for cementation microscopic parameters including stiffness, size, axial, and shear strength. The simulation results indicate that the CO 2 -related degradation of mechanical properties in bleached Entrada sandstone can be attributed to the reduction of cement size rather than cement strength. Finally, our study indicates that it is possible to describe the CO 2 -related rock alteration through particle-scale mechanisms.

54 ENVIRONMENTAL SCIENCES↗

AREA 2: Novel Materials for Robust Repair of Leaky Wellbores in CO 2 Storage Formations

The potential leakage of hydrocarbon fluids or CO 2 out of subsurface formations through wells with fractured cement or debonded microannuli is a primary concern in oil and gas production and CO 2 storage. The presence of fractures in a cement annulus with apertures on the order of 10–300 microns can pose a significant leakage danger with effective permeability in the range of 0.1–1 mD (millidarcy). Leakage pathways with small apertures are often difficult to repair using conventional oilfield cement, thus a low-viscosity sealant that can be easily placed into these fractures while providing an effective seal is desired. The development of a novel application using pH-triggered polymeric sealants could potentially be the solution to plugging these fractures and that was the research aim of this study. The application is based on the transport and reaction of a low-pH poly(acrylic acid) polymer through fractures in strongly alkaline cement. The pH-sensitive microgels viscosify upon neutralization with cement to become highly swollen gels with substantial yield stress that can block fluid flow. Experiments in a cement fracture determined the effects of the viscosification and gel deposition via real-time visual observation and measurements of pressure gradient and effluent pH. While the pH-triggered gelling mechanism and rheology measurements of the neutralized polymer gel show promising results, the polymer solution in contact with cement undergoes an undesirable reaction known as polymer syneresis. Syneresis is caused by the release of calcium cation from cement that collapses the polymer network. Syneresis produces an unstable calcium-precipitation byproduct that is detrimental to the strength and stability of the gel in place. As a result, gel-sealed leakage pathways that subjected to various degrees of syneresis often failed to hold back pressures. Several chemicals were studied to inhibit polymer syneresis and tested for pretreatment of cement cores to remove calcium and prevent syneresis during polymer placement. A chelating agent, sodium triphosphate (Na 5 P 3 O 10 ), was found to successfully eliminate syneresis without compromising the injectivity of polymer solution during placement. Polymer gel strength is determined by recording the maximum holdback pressure gradients during liquid breakthrough tests after various periods of pretreatment and polymer shut-in time. Cores pretreated with Na 5 P 3 O 10 successfully held up to an average of 80 psi/ft, which is significantly greater than the expected threshold value of about 0.1-5 psi/ft required to prevent flow in a typical CO 2 leakage scenario. The use of such inexpensive, pH-triggered poly-acrylic acid polymer allows long-term robust seal of leaky wellbores under high pH conditions.

01 COAL, LIGNITE, AND PEAT↗

Novel ductile wellbore cementitious composite for geologic CO 2 storage

CO 2 leakage through damaged wellbore cement sheaths is a major risk of geologic CO 2 storage (GCS), as conventional wellbore cement is brittle and can be damaged due to acid attack and downhole stresses during CO 2 injection. Here we examine a novel fiber-reinforced engineered cementitious composite (ECC) proposed as a substitute to conventional wellbore cement due to its superior ductility and intrinsic crack width control. ECC and conventional wellbore cement coupons were exposed to water in equilibrium with CO 2 at 50 °C and 10 MPa. The samples were retrieved after several days and their mechanical performance was evaluated using a four-point bending test, microhardness, and compressive strength analyses. Optical microscopy and mercury intrusion porosimetry were used to characterize the progression of the carbonation front and pore structures of the specimens. Control experiments were conducted under the same temperature and pressure conditions but with a N 2 headspace to isolate the impact of CO 2 . It was found that carbonation increased the ultimate flexural strength of ECC but decreased its ductility. However, the ductility of carbonated ECC remained higher than that of conventional wellbore cements that exhibited brittle failure under all test conditions. Additionally, ECC exhibited minimal material loss and continued resistance to deformation in comparison to conventional wellbore cements. This suggests that while the exposure of ECC to CO 2 will alter its mechanical properties, altered ECC will continue to exhibit mechanical performance superior to conventional wellbore cement, and therefore shows promise as a highly durable wellbore cementing material for GCS applications.

58 GEOSCIENCES↗

Feasibility of Algal Biochar, a Byproduct of Biofuel Production, as a Supplemental Cementitious Material

Algal biochar, as the solid residue of biofuel production from algal biomass, is reported to explore disposition options, aiming to lessen the liability or obstacles to biofuel production processes. However, landfills and open combustion lead to adverse environmental impacts. One way to add value to such wastes is to use them as admixtures in cementitious construction materials. This study aims to investigate the feasibility of algae-derived biochar as supplementary cementitious materials (SCM) at different water contents and mixture ratios. Algal biochar-cement composites were prepared with different algal biochar content as well as different water-to-cement (w/c) ratios, and the surface area, morphology, elemental, and mineralogical composition were characterized. To compensate for the high-water absorption of algal biochar, a small concentration of a superplasticizer was used since higher w/c ratios negatively impact strength. The mechanical performance of algal biochar-cement composites is compared with control composites using commercial silica fume as a typical commercial SCM. The findings suggest that algal biochar is a promising candidate to replace commercial SCM, like silica fume, since algal biochar-cement composites can reach comparable compressive strength and Young’s modulus to commercial pozzolan-cement materials with the same w/c ratio, though at later curing times, 33 days. Although the tensile strength of algal biochar-cement composites is statistically similar at 7 days, it is significantly lower at later curing times, and further investigation is required to improve this property. Algal biochar-based cement binders showed comparable embodied carbon to silica fume-based cement binders based on a cradle-to-gate lifecycle analysis. However, the ability of algal biochar to absorb large volumes of CO 2 over short periods of time, as measured in this study, makes this novel SCM an excellent alternative to reduce the embodied carbon of concrete structures cradle-to-grave at 1/10 of the cost. In conclusion, valorization of algae-derived solid waste provides great potential to reduce embodied carbon and brings credit to biofuel production and concrete-based construction.

algae-derived↗

SCM Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

This report summarizes experimental work performed by SIMCO Technologies Inc. (SIMCO) as part of the Cementitious Barriers Partnership (CBP) project. The test series followed an experimental program dedicated to the study of ordinary Portland cement (OPC) hydrated cement pastes exposed to aggressive solutions. In the present study, the scope is extended to hydrated cement pastes incorporating supplementary cementitious materials (SCM) such as fly ash and ground granulated blast furnace slag (GGBFS). Also, the range of aggressive contact solutions was expanded. The experimental program aimed at testing aggressive contact solutions that more closely mimic the chemical composition of saltstone pore solution. Five different solutions, some of which incorporated high levels of carbonate and nitrate, were placed in contact with four different hydrated cement paste mixes. In all solutions, 150 mmol/L of SO 4 2– (14 400 ppm) were present. The solutions included different pH conditions and different sodium content. Two paste mixes were equivalent to Vault 1/4 and Vault 2 concrete mixes used at SRS in storage structures. Two additional paste mixes, cast at the same water-to-cement ratio and using the same cements but without SCMs, were also tested. The damage evolution in samples was monitored using ultrasonic pulse velocity (UPV) and mass measurements. After three and twelve months of exposure conditions, samples were taken out of solution containers and analyzed to perform migration tests and porosity measurements. Globally, results were in line with the previous study and confirmed that high pH may limit the formation of some deleterious phases like gypsum. In this case, ettringite may form but is not necessarily associated with damage. However, the high concentration of sodium may be associated with the formation of an AFm-like mineral called U-phase. The most significant evidences of damage were all associated with the Vault 2 paste analog. This material proved very sensitive to high pH. All measurement techniques used to monitor and evaluate damage to samples indicated significant alterations to this mix when immersed in contact solutions containing sodium hydroxide. It was hypothesized that the low cement content, combined with high silica content coming from silica fume, fly ash and GGBFS led to the presence unreacted silica. It is possible that the pozzolanic reaction of these SCMs could not be activated due to the low alkali content, a direct consequence of low cement content. In this scenario, the material end up having a lot of silica available to react upon contact with sodium hydroxide, possibly forming a gel that may be similar to the gel formed in alkali-silica reactions. This scenario needs further experimental confirmation, but it may well explain the poor behavior of mix PV2 in presence of NaOH.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Intrinsic self-stressing and low carbon Engineered Cementitious Composites (ECC) for improved sustainability

Highlights: • A self-stressing criterion for ECC was established and experimentally verified. • An intrinsic self-stressing ECC was developed by utilizing LC3 and CSA cement. • Initial maximum expansion and later expansion loss were successfully tailored. • Expansion mechanism was identified by XRD patterns. • Self-stressing ECC has 64% of the carbon footprint of conventional concrete. Engineered Cementitious Composites (ECC) is an emerging cementitious composite material with ultra-high ductility. However, its higher cement dosage limits its material greenness and leads to concerns with drying shrinkage. In this research, an ECC utilizing limestone calcined clay cement (LC3) and calcium sulphoaluminate cement (CSA) is investigated, focusing on minimizing the material's embodied carbon while enhancing its durability with intrinsic self-stressing functionality. A self-stressing criterion is theoretically established and experimentally verified. X-ray diffraction patterns reveal an ettringite quantity that modulates the initial expansion and later expansion-reversal of LC3-CSA-ECC to support a persistent self-stressing mechanism. LC3-CSA-ECC has a lower (64%) carbon footprint and similar embodied energy compared to conventional concrete. When combined with the durability advantage (tiny crack, high ductility of 5.5%, and self-stressing function), this low carbon self-stressing ECC holds promise as a sustainable repair material that lowers the embodied and operational carbon in civil infrastructure.

36 MATERIALS SCIENCE↗

Progress and Challenges in Self-Healing Cementitious Materials

Concrete is the most used man-made material today consisting of a mixture of aggregates (sand, gravel, crashed rock) and paste. The paste component, made up of cement and water, cracks with time. Despite this shortcoming, research towards next-generation cement and concrete has only taken a boost in the past 10-15 years. In particular, self-healing cementitious materials is a research area that has attracted a great deal of attention. A number of reported novel formulations have demonstrated an increase in mechanical and chemical stability with respect to conventional Portland cement, through the addition of inorganic, organic, and even biological additives. This review reports on the latest advances in cement research related to the synthesis of self-healing cements applied in concrete structures. These include geopolymers, engineered cementitious materials (ECC), bacterial cement composites, microencapsulated self-healing materials, shape memory alloys (SMA), and polymer-cement composites. This work describes the performance of each cementitious material and the mechanism responsible for self-healing, including a section on the latest computational modeling studies towards this end. A detailed understanding of these various self-healing cement technologies, including their strengths and weaknesses, is critical at the time of determining the type of structures that these materials could be used for.

Fernandez, Carlos A.↗

A new polymer nanocomposite repair material for restoring wellbore seal integrity

Seal integrity of functional oil wells and abandoned wellbores used for CO 2 subsequent storage has become of significant interest with the oil and gas leaks worldwide. This is attributed to the fact that wellbores intersecting geographical formations contain potential leakage pathways. One of the critical leakage pathways is the cement-shale interface. In this study, we examine the efficiency of a new polymer nanocomposite repair material that can be injected for sealing micro annulus in wellbores. The bond strength and microstructure of the interface of Type G oil well cement (reference), microfine cement, Novolac epoxy incorporating Neat, 0.25%, 0.5%, and 1.0% Aluminum Nanoparticles (ANPs) with shale is investigated. Interfacial bond strength testing shows that injected microfine cement repair has considerably low bond strength, while ANPs-epoxy nanocomposites have a bond strength that is an order of magnitude higher than cement. Microscopic investigations of the interface show that micro annulus interfacial cracks with widths up to 40 μm were observed at the cement-shale interface while these cracks were absent at the cement-epoxy-shale interface. Finally, Fourier Transform Infrared and Dynamic mechanical analysis measurements showed that ANPs improve interfacial bond by limiting epoxy crosslinking, and therefore allowing epoxy to form robust bonds with cement and shale.

36 MATERIALS SCIENCE↗

Assessment of Cementitious Composites for High-Temperature Geothermal Wells

High-temperature (HT) geothermal wells can provide green power 24 hours a day, 7 days a week. Under harsh environmental and operational conditions, the long-term durability requirements of such wells require special cementitious composites for well construction. This paper reports a comprehensive assessment of geothermal cement composites in cyclic pressure function laboratory tests and field exposures in an HT geothermal well (300–350 °C), as well as a numerical model to complement the experimental results. Performances of calcium–aluminate cement (CAC)-based composites and calcium-free cement were compared against the reference ordinary Portland cement (OPC)/silica blend. The stability and degradation of the tested materials were characterized by crystalline composition, thermo-gravimetric and elemental analyses, morphological studies, water-fillable porosity, and mechanical property measurements. All CAC-based formulations outperformed the reference blend both in the function and exposure tests. The reference OPC/silica lost its mechanical properties during the 9-month well exposure through extensive HT carbonation, while the properties of the CAC-based blends improved over that period. The Modified Cam-Clay (MCC) plasticity parameters of several HT cement formulations were extracted from triaxial and Brazilian tests and verified against the experimental results of function cyclic tests. These parameters can be used in well integrity models to predict the field-scale behavior of the cement sheath under geothermal well conditions.

15 GEOTHERMAL ENERGY↗

Quality design of belite–melilite clinker

We have developed a new cement clinker, consisting mainly of belite and melilite, which is capable of increasing the amount of recycled waste as a part of its raw materials. We analyzed clinkers with a wide range of compositions, and clarified the quantitative relationship between the chemical and mineral compositions. Clinkers consisting mostly of belite and melilite were successfully obtained at the CaO/SiO{sub 2} mass ratio of 1.7 to 1.9. Test cements were prepared using these clinkers and mixed with OPC for the evaluation of fluidity and strength. The belite–melilite cement was found to have good fluidity, and the belite–melilite cement mixed with OPC at up to 30% exhibited a satisfactory long term strength equivalent to the OPC, demonstrating the potential as an alternative to OPC. Electron probe microanalysis revealed the relatively high concentration of diphosphorus pentaoxide in belite, suggesting this component might contribute to the strength enhancement of the cement. -- Highlights: •A new cement clinker consisting mainly of belite and melilite was designed. •The clinker enables the use of various recycled wastes as part of its raw materials. •The relationship between the chemical and mineral compositions was clarified. •This cement mixed with OPC at up to 30% exhibited a good quality equivalent to OPC.

36 MATERIALS SCIENCE↗

Modelling of the sulfuric acid attack on different types of cementitious materials

A chemical-reactive transport model is used to simulate the sulfuric acid attack of cement pastes based on ordinary Portland cement (CEM I), blended Portland cements (CEM III, CEM IV, and CEM V), and calcium aluminate cement (CAC). This model accounts for the dissolution of cement hydrates (portlandite, C-S-H, hydrogarnet), and the precipitation of deterioration products (ettringite and gypsum). Moreover, diffusion of the aqueous species in the pore space of the material is considered. With this model, the hydrate contents, the porosity, and the deterioration phase contents throughout a sulfuric acid attack are determined. Two indicators are defined to predict the service life of the cementitious materials: the deterioration depth and the dissolved calcium content. These two indicators show that calcium aluminate cement has a better resistance to sulfuric acid attack than that of Portland cements. This better resistance is mainly due to the partial dissolution of CAC hydrate as opposed to the total dissolutions of CH and C-S-H.

36 MATERIALS SCIENCE↗

Simulation of axial tensile well deformation during reservoir compaction in offshore unconsolidated methane hydrate-bearing formation

Sand production encountered in the 2013 offshore field gas production tests at the Nankai Trough, Japan, could be attributed to well failure during reservoir compaction. In this study, well integrity under various reservoir compaction patterns for the Nankai Trough case is examined using a well-formation finite element model. Here, the modelling details include the inclusion of a cement sheath as well as the modelling of construction processes (such as cement shrinkage). Well elongation in the overburden layer becomes significant when the reservoir subsidence is localized near the wellbore under large depressurization. Results show that the maximum plastic deviatoric strain level in the cement could reach 0.7% when the maximum reservoir subsidence reaches 0.85 m and cement shrinkage is limited. When cement shrinkage rises to 0.75%, the maximum plastic deviatoric strain increases to 2.4% as the cement accumulates additional plastic strain during shrinkage due to its deformation being constrained by the casing. In order to prevent the cement from failure, it might be effective to hold the pressure drawdown at a low level (e.g., several MPa) until the hydrate dissociation front advances to a certain radius from the well (e.g., a couple of tens of metres).

58 GEOSCIENCES↗

High-performance cementitious composites containing nanostructured carbon additives made from charred coal fines

Carbon-based nanomaterials, such as carbon nanoplatelets, graphene oxide, and carbon quantum dots, have many possible end-use applications due to their ability to impart unique mechanical, electrical, thermal, and optical properties to cement composites. Despite this potential, these materials are rarely used in the construction industry due to high material costs and limited data on performance and durability. In this study, domestic coal is used to fabricate low-cost carbon nanomaterials that can be used economically in cement formulations. A range of chemical and physical processing approaches are employed to control the size, morphology, and chemical functionalization of the carbon nanomaterial, which improves its miscibility with cement formulations and its impact on mechanical properties and durability. At loadings of 0.01 to 0.07 wt.% of coal-derived carbon nanomaterial, the compressive and flexural strength of cement samples are enhanced by 24% and 23%, respectively, in comparison to neat cement. At loadings of 0.02 to 0.06 wt.%, the compressive and flexural strength of concrete composites increases by 28% and 21%, respectively, in comparison to neat samples. Additionally, the carbon nanomaterial additives studied in this work reduce cement porosity by 36%, permeability by 86%, and chloride penetration depth by 60%. These results illustrate that low-loadings of coal-derived carbon nanomaterial additives can improve the mechanical properties, durability, and corrosion resistance of cement composites.

36 MATERIALS SCIENCE↗

Quantification of Wellbore Leakage Risk Using Non-destructive Borehole Logging Techniques

Well integrity is important at all potential CCS locations and may play a crucial role establishing leakage risk in areas where there is a high density of existing wells that could be impacted by the storage operations including depleted petroleum fields where EOR or CCS will occur. To address a need for risk quantification methods that can be directly applied to individual wells using borehole logging tools a study was conducted using data from five wells in Wyoming. The objectives of the study were: Objective 1: Develop methods to establish the baseline flow parameters (porosity and permeability or mobility) from individual measurements of the material properties and defects in a well. Objective 2: Develop a correlation between field flow-property data and cement logs that can be used to establish the flow-properties of well materials and well features using cement mapping tools. Objective 3: Establish a method that uses the flow-property model (Objective 2) to analyze the statistical uncertainties associated with individual well leakage that can provide basis for uncertainty in risk calculations. The project objectives were met through the logging of five wells in Carbon and Natrona County Wyoming to collect data that was used to estimate individual and average well flow properties and model the results using ultrasonic data collected during the logging. Three of the five wells provided data on point and average flow properties for well annuli. Data from the other two wells were used to create models of cement permeability and test whether information collected in one well could be used to characterize another well. The results of the in-situ point measurements were confirmed by the lab measurements sidewall cores collected near the same depths Objective 1 was met using the data collected through logging, testing, and sampling. The methods were developed that can establish baseline flow parameters of wells by both point and average test methods. The methods to estimate the flow properties modeling of point pressure tests, modeling of vertical interference tests, and laboratory measurement of cased-hole sidewall cores The wells were in sufficiently good shape to allow the development of the characterization methods while still having enough defects to study differences in results as they relate to well integrity. Samples and tests analyzed from three of five wells studied in showed the cements were largely intact and had not degraded from exposure native brines. Log results taken in conjunction with the core measurements indicate that interfaces and/or problems with cement placement due to eccentering provide preferential flow paths for fluids, which can increase the effective permeability of the barrier several orders of magnitude above the permeability of intact cement. The results of the maps created using logging tools indicating that the cement condition and bond are generally good identify a need for more research to understand how logs can be used to predicteffective well permeabilities such as those measured by the VITs in this study.

42 ENGINEERING↗

Wellbore Seal Repair Using Nanocomposite Materials

Nanocomposite wellbore repair materials have been developed, tested, and modeled through an integrated program of laboratory testing and numerical modeling. Numerous polymer-cement nanocomposites were synthesized as candidate wellbore repair materials using various combinations of base polymers and nanoparticles. Based on tests of bond strength to steel and cement, ductility, stability, flowability, and penetrability in opening of 50 microns and less, we identified Novolac epoxy reinforced with multi-walled carbon nanotubes and/or alumina nanoparticles to be a superior wellbore seal material compared to conventional microfine cements. A system was developed for testing damaged and repaired wellbore specimens comprised of a cement sheath cast on a steel casing. The system allows independent application of confining pressures and casing pressures while gas flow is measured through the specimens along the wellbore axis. Repair with the nanocomposite epoxy base material was successful in dramatically reducing the flow through flaws of various sizes and types, and restoring the specimen comparable to an intact condition. In contrast, repair of damaged specimens with microfine cement was less effective, and the repair degraded with application of stress. Post-test observations confirm the complete penetration and sealing of flaws using the nanocomposite epoxy base material. A number of modeling efforts have supported the material development and testing efforts. We have modeled the steel-repair material interface behavior in detail during slant shear tests, which we used to characterize bond strength of candidate repair materials. A numerical model of the laboratory testing of damaged wellbore specimens was developed. This investigation found that microannulus permeability can satisfactorily be described by a joint model. Finally, a wellbore model has been developed that can be used to evaluate the response of the wellbore system (casing, cement, and microannulus), including the use of either cement or a nanocomposite in the microannulus to represent a repaired system. This wellbore model was successfully coupled with a field-scale model of CO 2 injection, to enable predictions of stress and strains in the wellbore subjected to subsurface changes (i.e. domal uplift) associated with fluid injection.

36 MATERIALS SCIENCE↗

Advanced Downhole Acoustic Sensing for Wellbore Integrity (Final Report)

Borehole cement is used across the range of energy technologies to stabilize casing, to serve as a barrier to behind-casing fluid movement. Cement debonding and other flaws, both at cement interfaces and within the cement itself, can create leakage pathways that can threaten safety to personnel, and wellbore performance, with economic and regulatory consequences. A primary method to assess cement health and wellbore integrity is via acoustic methods. This project was designed with three aims: demonstrate a significant improvement in the interpretation of cement acoustic behavior, both during curing, and in interpreting effects of flaws and evolving interfaces; develop sensor technologies to improve signal-noise ratios and cement acoustic responses; and lastly, provide a borehole demonstration of at least one of these technologies. We have accomplished the first two objectives, and the third, delayed by pandemic health concerns, is proceeding as of this writing via a technology partner with the University of Texas Advanced Energy Consortium.

15 GEOTHERMAL ENERGY↗

Achieving Unprecedented CO 2 Utilization InCO 2 Concrete™: System Design, Product Development and Process Demonstration

Anthropogenic sources of carbon dioxide are generated from a number of sources, but the key among these are ordinary Portland cement (OPC) production and combustion of fossil fuels. Cement production is the largest global CO 2 source from the mineral decomposition of carbonates. This is due to the clinkering process whereby limestone (mainly consisting of CaCO 3 ) is decomposed into CaO and CO 2 , and combined with silica rich clays at high temperatures to form clinkers (i.e. the four key minerals that comprise cement). The high temperature range of 1400 – 1550°C required for this process accounts for up to 60% of the generated CO 2 from cement production. Combination of the limestone decomposition and thermal requirements of the clinkering process causes cement production to contribute 8-9% of annual global CO 2 emissions. Combustion of fossil fuels (coal, oil and gas) was shown to contribute a much larger portion of global CO 2 emissions. As of 2018, combustion of fossil fuels accounted for 65% of global CO 2 , where 41% was derived from stationary sources for electricity and heat generation and the other 24% was related to transport. To reduce these contributions, key steps forward in CO 2 utilization technologies are required. Therefore, a CO 2 mineralization technology (CO 2 mineralization concrete) to reduce the OPC content in concrete, while utilizing flue gas emissions from fossil fuel combustion has been developed to address both areas simultaneously. This Reversa™ technology utilizes low-carbon cementation agents produced by in situ CO 2 mineralization (“mineral carbonation reactions”) to offer a promising alternative to OPC. CO 2 mineralization relies upon the reaction of dissolved CO 2 with inorganic alkaline reactants to precipitate mineral carbonates (e.g., CaCO 3 ), which bind proximate particles and achieve cementation. Herein, a concrete green body, which is composed of a mixture of binder, water, and mineral aggregates, is exposed to CO 2 borne in industrial flue gas streams. This manner of CO 2 mineralization allows the production of construction components that feature equivalent engineering attributes as their OPC-based counterparts while featuring a much smaller embodied carbon intensity (eCI). The purpose of this project is to demonstrate the feasibility of the Reversa process evolving from a TRL-3 technology at the bench-scale up to TRL-6 technology at the pilot-scale. The reliability of the Reversa technology was tested to prove the effective production of three standard industrial concrete products selected during the course of the project. The results detailed herein will demonstrate the evolution of this technology to the industrial scale. The culmination of this work resulted in 9 production runs completed at the National Carbon Capture Center (NCCC), Wilsonville, AL, using natural gas (NG) flue gas as the CO 2 source. Over the course of the production runs at NCCC, the CO 2 utilization as a function of time, 24-h CO 2 uptake, electricity usage, and 28-d net area compressive strength recorded for each run. Collection of this data will be used to determine the success of the demonstration goals: (1) achieving in excess of 0.2gCO 2 /g reactant , (2) achieving greater than 50% reduction in global warming potential compared to standard produced units, and (3) ensuring compliance of carbonated concrete with industry standard specifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TRIDENT Drill Validation at Mars and Lunar Analog Field Sites

Drilling on Earth is typically a human-intensive activity. Drilling on other planets is further complicated by the lack of prior local field surveys of their target area, hence blindly drilling into uncertain target rocks. Field conditions on the Moon or Mars are also different than for shallow drilling on Earth: lower temperatures and pressures, less power available, low masses (hence less weight-on-bit). Given the cost of transport from Earth, no drilling muds or working fluids are likely to be available to carry away cuttings. And impact-gardened regolith and dust vary mechanically and texturally from most terrestrial soils. The Regolith and Ice Drill for Exploration of New Terrains (TRIDENT) is a rotary-percussive 1m-class drill from Honeybee Robotics. It is low-power (rotary and percussive actuators are 200 W each) and lightweight (<20 kg) with the maximum weight on bit limited to 200 N. TRIDENT has been manifested for the Volatiles Investigating Polar Exploration Rover (VIPER) and PRIME-1 lunar south pole missions in 2024, has previously been field tested at a hot, dry analog site in the Atacama Desert, and in lunar conditions in thermal vacuum chamber tests. TRIDENT was also part of the 2019 Icebreaker Mars Discovery proposal, as well as in the Mars Life Explorer concept. During ARADS tests, drill control and fault recovery automation software enabled hands-off operations of a rover-mounted TRIDENT drill. TRIDENT Drill Analog Site Validation: Past TRIDENT tests in thermal vacuum (TVAC) chambers targeted containers of manufactured lunar simulants with added volatiles. 2022 TRIDENT ambient testing at NASA Ames drilled into cemented lunar simulant materials. Low cuttings-permeability led to cuttings buildup, and drill choking and binding was observed. The Atacama analog site in ARADS had desiccated unconsolidated sediments that did not challenge the TRIDENT design. However, lunar polar regolith is expected to be diverse and heterogeneous with varying clast sizes, with abundant impactites and perhaps subsurface ice deposits. Neither the simulants nor Atacama testing had completely covered the TRIDENT-targeted field characteristics, motivating further analog tests prior to the planned lunar missions. To gain more insight into the behavior of the TRIDENT hardware in diverse impactites and subsurface ice, and to verify the software automation in that environment, in August 2023 TRIDENT was brought to Haughton Crater, a field analog site in the Canadian Arctic. In September 2023 the same drill was brought to the Bishop Tuff in southern California to verify whether drilling binding behaviors previously seen in lunar simulant testing would be observed in naturally occurring fine-grained massive layers. The ~22 Ma Haughton Crater impact structure is located at 75 ̊22’ N, 89 ̊41’ W, on northwestern Devon Island, Nunavut, Canada. Numerous deposits of pale-grey crater-fill polymictic impact-melt breccia are found within the crater with a typical thickness reaching ~125 m or greater and covering ~60 km -2 . An approximately 600m-thick permafrost layer is also present with ice typically found within 0.5-0.6m of the surface. The volcanic tableland north of Bishop, CA exposes densely welded tuff laid down during the eruption that created the Long Valley Caldera at approximately 0.76 Ma. Extensional faults and the Owens River gorge expose cross-sections across the plateau. The area is viewed as an analog site for Mars features believed to be of pyroclastic origin. Results: Haughton Crater.Drilling tests were conducted 8-13 August 2023 at a previously undisturbed area separated 5-10 m from past years’ Drill Hill test sites (75.4208, -089.7613). In six days, TRIDENT drilled 8 holes to nearly 1 m depth each, totaling 7.80 m. The active layer/ice boundary was at ~67 cm depth, with a total of approximately 2.4 m drilled into ice or ice-cemented impact breccia. During drilling, five drill fault states were observed and successfully recovered. Holes 23-1, 4 and 7 were drilled under manual control, using Honeybee’s Thorax user interface. Holes 23-5, 6, and 8 were drilled with the Ames IBexec automated drilling control software. TRIDENT was observed to have little difficulty in the thawed uncemented impact breccia above the active layer boundary, but required percussion to make slower headway in the ice-cemented breccia. In Hole 23-7 (Fig.1), drilling slowed down in a massive unit just above the active-layer boundary (perhaps a large rock extending into the ice-cementation?), with only 7cm progress made in 27 minutes of high auger torque and constant percussion, leading to a choking fault and then a binding fault. A similar pattern had been observed in TRIDENT Rio Tinto test data from 2017 [6] as well as in the 2022laboratory tests.Bishop Tuff.A team from NASA Ames and the US Geological Survey deployed the same TRIDENT drill to Bishop Sites 1B and 1C (37.4203, -118.4289; 37.4265, -118.4215) on 13-16 September 2023, on the Bishop Tuff plateau. A third drill site was used 17-18 September 2023(37.4598, -118.3667) in an abandoned pumice mine. Four holes (totaling 2.5m depth) were drilled into the fine-grained, meters-thick tuff units at Sites 1B and 1C, and a further two boreholes (totaling 1.98m depth) were made at the pumice site. Drill behavior in the tuff below 10 cm depth was similar to that seen at 65-74 cm depth in Haughton Hole 23-7 (Fig. 1) and that seen in the 2022 lab simulant drilling. Drill safety torque limits were exceeded multiple times resulting in drill stops downhole. These freezes then required external added torques (with a pipe wrench) to resume rotation, to unstick the drill for withdrawal. To prevent this choking and binding behavior we found that more-frequent cuttings removal was necessary, e.g., reducing the “drill bite” size from the nominal 10 cm to 2 cm per bite --bringing the auger up to the surface more frequently, as seen in Bishop Site 1C Hole 2 (Fig.2). This permitted slow progress without drill binding and without external interventions. Conversely, TRIDENT drilling in the more porous pumice target material showed no cuttings buildup issue, and single bites as large as 40 cm were demonstrated. Discussion: We observed that TRIDENT easily penetrated unconsolidated heterogeneous soils (both above the active layer boundary at Haughton and previously in the Atacama). Cemented or consolidated targets that were cuttings-permeable (icy impact breccia, pumice) required more energy applied and percussion. However, in non-cuttings-permeable targets (welded microporous tuff, cemented simulants, boulder) TRIDENT was observed to be prone to excessive cuttings accumulation leading to choking/binding faults and stalling. The wedge cutting bit, used by TRIDENT in field tests and in its flight versions, pulverizes the target rock and creates fine cuttings that ideally are transported up the auger spirals for removal. In porous, fractured or vesicular target materials (such as at the Bishop pumice site) a significant portion of the cuttings are pushed aside, but for non-fractured, microporous targets the cuttings remain in the borehole and accumulate. Rock powder is relatively incompressible as a working fluid at only 100-200N downward force (TRIDENT limits) and hence eventual drilling progress slows or stops. Our recommended strategy for improving TRIDENT cuttings removal in massive target units with low cuttings-permeability is to reduce TRIDENT bite sizes when encountering these units, from 10cm to as little as 1-2cm, to effectively bail the accumulating cuttings. This approach was demonstrated to reduce choking and allowed slow progress to continue in cuttings-impermeable microporous target units (viz. the Bishop tuff in our September 2023 tests or cemented simulants in 2022 ambient tests).

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