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At least 145 records · Page 8

Biopolymer Modified Cementitious Systems with Radically Superior Strength and Durability

This project was a pioneering study of the effect of nanochitin additives on setting time, rheological, and mechanical properties of cementitious materials. Chitin is the second most abundant biopolymer in nature after cellulose and is readily available from byproducts of the growing seafood industry. In this study, chitin powder from shrimp shells was processed into chitin nanocrystals (ChNCs) and chitin nanofibers (ChNFs). Ch-Cs delayed initial and final set times with their high ionic surface charges likely by electrostatic repulsion. The viscosity of fresh cement paste increased with Ch-NFs, while Ch-NCs did not significantly affect rheological properties. The distinct effects of the two nanochitin forms are attributed to the mobility of the different morphologies of the rod-like ChNCs vs. the entangled and restrained network of the ChNFs. Nanochitin forms showed encouraging results by significantly increasing flexural strength by ~40% at the optimum concentration of 0.05 wt% and significant increases in fracture energy. These bio-additives were found promising and future studies should continue to evaluate their use in concrete.

36 MATERIALS SCIENCE↗

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↗

Facilitating Implementation of High-Volume Fly Ash Use in Pre-cast Concrete Construction to Increase Beneficial Utilization

The main goal of this project was to increase the beneficial use of fly ash as a supplementary cementitious material for precast concrete applications. A major focus was to develop balanced concrete mix design strategies which collectively satisfy the follow objectives: 1) increase fly ash beneficial use by at least 15% in the precast concrete industry, 2) maintain or exceed stringent structural property requirements (e.g., compressive strength at initial prestress, modulus of rupture, etc.), 3) exhibit little or no additional cost relative to conventional mixtures, and 4) mitigate detrimental environmental consequences inadvertently caused by increased beneficial use. Outcomes from this project include recommendations for design guidelines and code provisions for sustainable concrete mix designs, facilitating diversion and harvesting of large quantities of fly ash from landfills or impoundments, and multiple frameworks for incorporating discarded fly ash materials (i.e., landfilled or ponded fly ash after separating the impurities) in concrete construction.

01 COAL, LIGNITE, AND PEAT↗

ASSESSMENT OF HIGH-VOLUME HARVESTED FLY ASH BLENDS FOR USE IN PRECAST CONSTRUCTION

Declining supplies of fresh fly ashes in some regions have further driven the importance of using harvested fly ash as a supplementary cementitious material and thus replacement for more energy-intensive ordinary Portland cement (OPC). Higher replacement rates of OPC with fly ash in general has traditionally been limited in precast operations due to stringent early-age strength requirements necessitated by initial prestress and lifting/handling of hardened components – often well within 24 hours after fresh concrete placement. Therefore, a series of mix designs were developed, as part of a larger framework for reassessing high-volume fly ash (HVFA) use in the context of precast construction, to demonstrate the feasibility of using larger fractions of harvested fly ash in concrete formulations suitable for precast fabrication demands. More specifically, a target minimum 24-hour compressive strength of 24.1 MPa (3500 psi) was set, in accordance with conventional precast structural design checks, while increasing the fly ash content to 40% replacement of OPC – at least a 15% increase above the traditional limit of 25%. The effect of using more sustainable Type IL cement in contrast to conventional Type III Portland cement (the traditional standard for precast use) – both in conjunction with HVFA use – was also examined. Early-age mechanical properties including compressive strength, modulus of rupture, and modulus of elasticity were evaluated within the aforementioned early-age window. Lastly, corresponding design equations were then reassessed for their applicability with respect to the high-early strength HVFA mixes examined herein.

Gombeda, Matthew J.↗

Development of Magnesium Oxysulfate Formulation for SRPPF Aqueous Recovery Liquid Solidification

The liquid effluent from the Savannah River Plutonium Processing Facility (SRPPF) Aqueous Recovery Processes will be solidified into a stable form that is acceptable by Waste Isolation Pilot Plant (WIPP) for disposal. The current Aqueous Recovery flow sheet proposes to solidify the liquid effluent using a grout formula that was developed and tested for the former Waste Solidification Building process. This Portland cement based mixture results in a high pH (~13) leachate from the solidified waste form which is not acceptable to WIPP in the large quantities expected from production at SRPPF. Various cementitious materials were previously evaluated as alternative grout formulations to Portland cement and a MgO-based mix was identified as a promising alternative. A magnesium oxysulfate (MOS) cement formulation comprised of reactive magnesium oxide (MgO), anhydrous magnesium sulfate (MgSO 4 ), and sand, as a non-reactive heat sink provided good mixability, similar density to the original Portland-cement based mix, and a leachate pH of 9.4, within the assumed WIPP brine pH range. However, the MOS formulation exhibited an appreciable amount of heat generation, which resulted in premature setting of a large-scale test.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development of Calcined Clay/Calcium Sulfate Blends for Robust Performance of LC3 Concrete

This report documents the development of robust blends of calcined clays (CCs) with calcium sulfate (gypsum) for application in limestone calcined clay cement (LC3) systems. The U.S. cement industry faces supply chain constraints and high energy intensity, motivating the need for alternative supplementary cementitious materials. Calcined clays are abundant and highly reactive when properly processed, but their variable physical and chemical characteristics can negatively impact hydration balance, rheology, and admixture demand in LC3 concretes. To address this, five calcined clays, two Portland cements, ground limestone, gypsum, and a polycarboxylate dispersant were procured. Isothermal calorimetry and mini-cone flow tests were used to determine sulfate and dispersant demand. Results show that the addition of approximately 6.7% gypsum, relative to the calcined clay weight, consistently balanced sulfate consumption across the LC3 systems studied. Dispersant demand, however, varied significantly with clay source, demonstrating the need for tailored admixture strategies. These findings confirm that supplying CC–gypsum blends directly to concrete producers is a viable approach to overcoming current manufacturing constraints, enabling reliable fresh and hardened performance of LC3 concretes, and supporting broader adoption of calcined clays in the U.S. market.

36 MATERIALS SCIENCE↗

Advanced Self-Healing Polymer-Cement Composites for Geothermal Wellbore Application at 300 °C

Polymer-cement composites were formulated using two base cements and three polymers and evaluated as potential alternatives to conventional geothermal wellbore cementitious material. To mimic geothermal conditions these cement composites were cured at 300 °C and their mechanical properties, including compressive strength, Young modulus, shear bond strength to steel casing, and self-healing and re-adhering (to steel) capability were tested. To test thermal stability the samples were cured at 300 °C for up to 30 days followed by analysis of their mineralogy and chemical composition by X-ray diffraction spectroscopy (XRD), 13C NMR, and total organic carbon (TOC). These tests showed that all polymer composites formulated were thermally stable as supported by almost 100% TOC of the 300 ?C cured samples and presence of all the polymer signals in 13C NMR permeability tests performed before and after healing a longitudinal fracture base cements and polymer-cement composites gave lower (2nd/1st) permeability ratios with respect to base cements which suggests that introduction polymers result in self-healing composite materials. Curing two of the best performing polymer-cement composites for a period of 30 days at 300 °C maintained the self-healing capability. These advanced polymer-cement composites with higher mechanical stability, ductility and self-healing capability are promising alternatives to wellbore cement materials for geothermal and fossil energy applications.

polymer-cement, composite, wellbore, self-healing,↗

Influence of Borate on Sorption of Strontium and Barium to Calcium Silicate Hydrate - 20148

Radioactive waste with the decommissioning process at the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains borate with relatively high concentration. As with general low-level wastes, such waste is also assumed the solidification with cementitious materials which calcium silicate hydrate (C-S-H) is one of the main components. In this study, the sorption behavior of strontium (Sr) ions and barium (Ba) ions to C-S-H in the presence of borate was examined by the sorption experiments without drying process. In the sorption experiments, C-S-H was synthesized by the mixture of calcium oxide, fumed silica and a solution with setting the Ca/Si molar ratios to 0.4, 0.8, 1.2 and 1.6. The total amount of a solid phase was 1.5 g, and the total volume of the solution containing borate and adsorbed ions (Sr or Ba) was 30 mL. The concentration of borate was set to 0 M or 0.6 M and the sodium/boron (Na/B) ratios was set to 0.2 or 1.0 by mixing boric acid and sodium hydroxide. The concentration of Sr ions or Ba ions was adjusted to 1 mM. The sorption period was set to 7 days. In the results, the sorption ratios of Sr ions and Ba ions for C-S-H exceeded 80% under all experimental conditions, although the sorption competition of cations with Na ions and the inhibition of the C-S-H formation with generating borate compounds observed by Raman spectroscopy might slightly reduce the sorption of them. These suggest that cationic radionuclides will be immobilized by C-S-H contained in the cements even in the presence of borate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Predicting Saturated Hydraulic Conductivity over Time for Degrading Saltstone Vault Concrete - 20376

At the Savannah River Site (SRS), low-level liquid tank waste is mixed with cementitious materials to produce a solid, monolithic waste form referred to as saltstone. The liquid saltstone mixture is pumped into massive concrete structures referred to as saltstone disposal units (SDUs) for curing and long-term storage. SDUs are vaults made of high performance concrete forming a barrier between saltstone and the surrounding environment. Predicting the long-term performance of SDU vault concrete, as well as the saltstone material itself, is critical to understanding the potential releases of radionuclides to the surrounding environment as described in the Saltstone Disposal Facility (SDF) performance assessment (PA). The hydraulic conductivity profile for SDU vault concrete was conservatively assumed to degrade linearly from the initial saturated hydraulic conductivity of the intact concrete over a long period of time. The initial hydraulic properties of saturated SDU vault concrete have been measured, and the final hydraulic properties of degraded vault concrete are assumed to be the same as the porous backfill material that will surround the vault after closure. The assumed final condition of the vault concrete is also conservative in that it provides a greater estimate of water penetration through the vault than would generally be expected. Therefore, insights that provide more realistic but conservative estimates as to how degradation processes may change the hydraulic properties of the SDU vault concrete, the time dependent relationship of the vault concrete hydraulic properties to degradation (and thus time), and the final hydraulic properties of the vault concrete provides useful additions to the SDF PA. This paper focuses on the assumption that the saltstone vault concrete saturated hydraulic conductivity would decrease linearly as a function of degradation time; this assumption resulted from a worst-case, weighted (by relative layer thickness), arithmetic average of intact and backfill material hydraulic conductivities representing flow parallel to a layered system. This research indicates that the effective saturated hydraulic conductivity of the degraded SDU vault concrete should be based on the relative thickness-weighted geometric mean of the intact and degraded layers hydraulic conductivities. This alternative, which is supported extensively in the relevant literature and evaluated in this paper, leads to a more realistic and defensible estimate of the effective saturated hydraulic conductivity in degraded vault concrete while remaining conservative. The impact of using the more realistic estimate of the effective saturated hydraulic conductivity for the degraded concrete decreases the effective saturated hydraulic conductivity by up to several orders of magnitude for early times (i.e., when the SDU vault concrete is assumed degraded via sulfate attack and carbonation). This revised estimate of the effective saturated hydraulic conductivity has been implemented in the recently revised SDF PA. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Study of Epoxy Sealant Layer for Use in Tank Bottom Refurbishment for the DOE EM Tank Waste R&D Program

This study addresses the DOE National Laboratory Program on Hanford Tank Waste Cleanup Research and Development, focusing on tank waste retrieval, transport, and closure. Millions of gallons of high-level waste are stored in the double shell tanks (DSTs) at Hanford site. The waste is stored in the primary tank, while the secondary shell acts as a buffer between the primary tank and environment. The DSTs’ bottoms could be corroded due to the corrosive waste properties and contents. Therefore, they are being emptied, and refurbishment is needed before waste storage continues. SRNL addresses the refurbishment of still operational DSTs bottoms with a two-layer refurbishment approach. We propose that the bottom layer consists of a high-density cementitious material to shield the epoxy top layer from radioactive residuals, while the top layer serves as an epoxy sealant. This work focuses on the experimental evaluation on the formulation and testing of the epoxy layer.

Blue, Kareen [Savannah River National Laboratory (↗

Enabling thermal energy storage in structural cementitious composites with a novel phase change material microcapsule featuring an inorganic shell and a bio-inspired silica coating

Phase change material (PCM) microcapsules offer a promising approach for integrating PCM into building materials for efficient thermal energy storage. Here, this study presents the development of a novel PCM microcapsule specifically designed for incorporation into cementitious materials. The microcapsule consists of a low-cost PCM core derived from vegetable oil by-products and a durable inorganic shell made from cenosphere, a hollow fly ash generated from coal burning power plants. A novel process is developed to apply a silica coating to these cenosphere-based PCM microcapsules (CPCM), resulting in bioinspired-silica-coated CPCM microcapsules (BCPCM). This coating process draws inspiration from marine microorganism-based silica production and utilizes low-cost sodium silicate as a precursor, enabling eco-friendly and cost-effective manufacturing at ambient temperature and mild pH conditions. The morphology, chemical stability, and thermal properties of the BCPCM along with its thermo-mechanical performance in cementitious composites were comprehensively analyzed. Experimental results demonstrate successful silica deposition on BCPCM, leading to enhanced latent heat properties of the produced BCPCM. With the silica coating, BCPCM exhibits a 50 °C delay in thermal decomposition compared to CPCM, enhancing fire resistance and preventing premature PCM leakage of the microcapsule. The bioinspired silica coating effectively restores over 10% of the strength loss for each percent increase in CPCM incorporated into the mortar. The thermal performance experiments reveal that increasing the BCPCM content reduces temperature peaks and rates of temperature increase, indicating an improved capacity for thermal energy storage. This new PCM microcapsule provides a cost-effective solution to integrate thermal energy storage to cementitious material, as evidenced that over 30% of aggregates (in volume) can be replaced by the microcapsule without a drastic loss of strength.

25 ENERGY STORAGE↗

Evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperature

This work studies the evolution of elastic and thermal properties of cementitious composites containing micro-size lightweight fillers after exposure to elevated temperatures (up to 800 °C). A multiscale investigation is carried out to study the thermal degradation of cementitious composite materials at multiple scale levels: at cement past level, the dehydration kinetics of cement hydrates (i.e., C–S–H, CH and aluminate hydrates) and development of microcracks are studied as functions of exposure temperatures. The damage mechanism of the inclusion phases and damages within the interfacial transition zone (ITZ) under elevated temperature are also investigated. In addition, the change of mechanical (i.e., elastic moduli, compressive strengths) and thermal (thermal conductivities) properties are measured as functions of the exposure temperature. Based on the experimental studies, a multiscale thermal degradation model is developed where the thermal degradations of cement paste (including water composition, porosity, and solid phase changes), inclusion phases, and the interfaces are captured through a multiscale sub-stepping homogenization scheme. The thermal degradation model is validated through multiple sets of experimental data. Finally, the influence of key parameters including the particle size distribution of the inclusions, the chemical composition, as well as the effects of ITZ damage are studied.

36 MATERIALS SCIENCE↗

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↗

Calcium silicate hydrate colloid at different humidities: Microstructure, deformation mechanism, and mechanical properties

Calcium silicate hydrate (C-S-H) is the main hydration product of Portland cement, while fundamental questions persist regarding its colloidal structure and water content. In this work, we developed a full atomistic C-S-H colloid model and investigated the physical and mechanical properties at different gel water concentrations. Water confined in nanometer gel pores degrades the mechanical properties of C-S-H because of its hydrolysis effect. A “ductile to brittle” transition was observed in the C-S-H colloid model with increasing gel water contents, evolving from transgranular failure to intergranular fracture. The gel water confined in nanometer-sized pores displays glassy characteristics, and it acts as a lubricant and facilitates structure distortions during the deformation. We elucidated the topology effect of the hydrogen bond network on the evolution of the viscoelasticity of C-S-H at different humidities. In conclusion, this work sheds light on the role of water in C-S-H colloids from nanostructure perspectives.

36 MATERIALS SCIENCE↗

Incorporating PCM-enabled thermal energy storage into 3D printable cementitious composites

This paper delineates the feasibility of incorporating microencapsulated phase change materials (mPCM) into 3D printable cementitious composite materials. A comprehensive experimental program was carried out to evaluate the impacts of mPCM on the printability, microstructures, mechanical and thermal properties of cementitious 3D printing ‘inks’. Results showed that the mPCM affected the printability of the cementitious ink material based on its physical properties (e.g., particle size) and volume loading – at lower volume loadings, mPCM increased the flowability of the cementitious ink material while leading to increased compressive strength and thermal conductivity for the hardened printed material. However, further increase in mPCM dosage led to a decrease in printability and, therefore, decrease in compressive strength and thermal conductivity as compared to the reference mixture. Here the results also showed that the inclusion of mPCM influence the printing parameters. In general, the inclusion of higher volume contents of mPCM necessitates a higher extrusion rate to achieve a desirable extrudability. Lastly, a thermal network model was formulated for 3D printed mPCM charged building components (e.g., wall). The study shows that microencapsulated PCM materials have good potential to be used in 3D printable cementitious mixtures for improving the thermal and energy performance of 3D printed buildings.

36 MATERIALS SCIENCE↗

Utilizing lowly-reactive coal gasification fly ash (CGFA) to stabilize aggregate bases

This study explored the feasibility of utilizing lowly-reactive coal gasification fly ash (CGFA) for stabilizing road aggregate bases. Three types of aggregate stabilizers including the ordinary Portland cement (OPC)-CGFA, hydrated lime (CH)-CGFA and alkali-activated CH-CGFA were evaluated based on the performances of compacted base specimens. It was found that the OPC-CGFA stabilized bases showed better mechanical and durability properties while the CH-CGFA samples had low water stability and freeze-thaw durability due to the dissolution of unreacted CH. However, the reaction degree of CGFA associated with the performances of CH-CGFA stabilization could be considerably enhanced by the alkali-activation. The sustainability and economic feasibility analyses showed the use of CGFA could significantly reduce the CO 2 emissions and costs, highlighting the synergy between the recycling of CGFA and the construction of sustainable road bases. Here, a framework of selecting CGFA-based stabilizers for road bases was proposed considering the performance ratings of the material properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development and Characterization of Cementitious Waste Forms for Immobilization of Granular Activated Carbon, Silver Mordenite, and HEPA Filter Media Solid Secondary Waste

At the Department of Energy’s Hanford site, over 53 million gallons of chemically complex and radioactive wastes have been stored in 177 underground tanks. The Hanford Tank Waste Treatment and Immobilization Plant (WTP) is under construction and is designed to treat and immobilize these wastes. During operations of WTP, solid secondary wastes (SSWs) will be generated as a result of waste treatment, vitrification, off-gas management, and supporting process activities. SSW treatment processes and resulting disposal pathways for the final disposition form of the SSW are needed to support direct feed low activity waste (DFLAW) operations and facilitate continued operation of WTP. The SSWs produced through WTP operations are expected to include used process equipment, contaminated tools and instruments, decontamination wastes, high-efficiency particulate air (HEPA) filters, carbon absorption beds (granular activated carbon, GAC), silver mordenite (AgM) and spent ion-exchange resins. These waste streams are planned to be immobilized in a cementitious waste form and disposed of either as stabilized/blended (non-debris) or encapsulated (debris) in a cementitious waste form. Accordingly, cementitious waste forms from these streams were included in the 2017 Integrated Disposal Facility (IDF) Performance Assessment (PA). The input data used to represent these SSW forms in the 2017 IDF PA involved many assumptions and associated uncertainties. This data limitation was due to the lack of material- and site-specific data available for representative SSW materials in cementitious matrices. To verify the assumed values used in the IDF PA and fill this limitation in available data, Washington River Protection Solutions, LLC (WRPS), has initiated a program targeted toward gathering site specific data relevant to Hanford SSW disposal. The work within this report is a continuation of this ongoing program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗